From 5a44ca95fc17c64666a9fd734c038b1b684ce7bf Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 13 Dec 2021 22:21:15 +0000 Subject: [PATCH 01/71] Working HF integral read-in --- Project#01/fortran/geom_utils.f90 | 19 +- Project#03/fortran/Makefile | 29 + Project#03/fortran/const.F90 | 21 + Project#03/fortran/els.x | Bin 0 -> 53312 bytes Project#03/fortran/enuc.dat | 1 + Project#03/fortran/eri.dat | 912 +++++++++++++++++++++++ Project#03/fortran/geom.dat | 6 + Project#03/fortran/geom_utils.f90 | 43 ++ Project#03/fortran/input.dat | 43 ++ Project#03/fortran/main.F90 | 22 + Project#03/fortran/mux.dat | 45 ++ Project#03/fortran/muy.dat | 45 ++ Project#03/fortran/muz.dat | 45 ++ Project#03/fortran/parallel.F90 | 19 + Project#03/fortran/read_in_integrals.f90 | 199 +++++ Project#03/fortran/s.dat | 45 ++ Project#03/fortran/system.f90 | 10 + Project#03/fortran/t.dat | 45 ++ Project#03/fortran/v.dat | 45 ++ 19 files changed, 1592 insertions(+), 2 deletions(-) create mode 100644 Project#03/fortran/Makefile create mode 100644 Project#03/fortran/const.F90 create mode 100644 Project#03/fortran/els.x create mode 100644 Project#03/fortran/enuc.dat create mode 100644 Project#03/fortran/eri.dat create mode 100644 Project#03/fortran/geom.dat create mode 100644 Project#03/fortran/geom_utils.f90 create mode 100644 Project#03/fortran/input.dat create mode 100644 Project#03/fortran/main.F90 create mode 100644 Project#03/fortran/mux.dat create mode 100644 Project#03/fortran/muy.dat create mode 100644 Project#03/fortran/muz.dat create mode 100644 Project#03/fortran/parallel.F90 create mode 100644 Project#03/fortran/read_in_integrals.f90 create mode 100644 Project#03/fortran/s.dat create mode 100644 Project#03/fortran/system.f90 create mode 100644 Project#03/fortran/t.dat create mode 100644 Project#03/fortran/v.dat diff --git a/Project#01/fortran/geom_utils.f90 b/Project#01/fortran/geom_utils.f90 index 07b4bc8..a23dfe6 100644 --- a/Project#01/fortran/geom_utils.f90 +++ b/Project#01/fortran/geom_utils.f90 @@ -18,11 +18,26 @@ subroutine get_bond_lengths(natoms, coords, bondlengths) do i = 1, natoms-1 do j = i+1, natoms ! Diagonals set to 0.0 in allocation - bondlengths(i, j) = norm2(coords(:,i)-coords(:,j)) - bondlengths(j, i) = bondlengths(i, j) + bondlengths(j, i) = norm2(coords(:,i)-coords(:,j)) + bondlengths(i, j) = bondlengths(j, i) end do end do end subroutine get_bond_lengths + subroutine get_bond_angles(natoms, coords, bondlengths, angles) + integer, intent(in) :: natoms + real(p), intent(in) :: coords(:,:), bondlengths(:,:) + real(p), allocatable, intent(out) :: angles(:,:,:) + real(p), allocatable :: uvecs(3,:,:) + + allocate(uvecs(natoms, natoms), source=0.0_p) + do i = 1, natoms-1 + do j = i+1, natoms + ! Diagonals set to 0.0 in allocation + ! Column major - for efficient memory access use this ordering + uvec(:,j,i) + end do + end do + end module geom_utils diff --git a/Project#03/fortran/Makefile b/Project#03/fortran/Makefile new file mode 100644 index 0000000..3b90b22 --- /dev/null +++ b/Project#03/fortran/Makefile @@ -0,0 +1,29 @@ +# Flags for GNU +FFLAGS = -g -fcheck=all +FC = gfortran + +# Suffixes +.SUFFIXES: + .SUFFIXES: .f90 .F90 .o .mod + .f90.o: + $(FC) $(FFLAGS) -c $< + .f90.mod: + $(FC) $(FFLAGS) -c $< + .F90.o: + $(FC) $(FFLAGS) -c $< + .F90.mod: + $(FC) $(FFLAGS) -c $< + +# Declare all files +OBJ = const.F90 system.f90 read_in_integrals.f90 main.F90 + +# Rules for making +els.x: $(OBJ) + $(FC) $(FFLAGS) -o $@ $(OBJ) + +const.o const.mod: const.F90 + $(FC) $(FFLAGS) -c const.F90 + +# Clean +clean: + rm *.o *.mod els.x diff --git a/Project#03/fortran/const.F90 b/Project#03/fortran/const.F90 new file mode 100644 index 0000000..fca71a3 --- /dev/null +++ b/Project#03/fortran/const.F90 @@ -0,0 +1,21 @@ +module const + use, intrinsic :: iso_c_binding, only: c_int32_t, c_int64_t + + implicit none + + ! Integer types + integer, parameter :: int_32 = selected_int_kind(6) + integer, parameter :: int_64 = selected_int_kind(15) + + ! Real types + integer, parameter :: sp = selected_real_kind(6,37) + integer, parameter :: dp = selected_real_kind(15,307) + + integer, parameter :: p = dp + + ! Highest precision pi + real(p), parameter :: pi = 4.0_p * atan(1.0_p) + + real(p), parameter :: depsilon = 1.e-12_p + +end module const diff --git a/Project#03/fortran/els.x b/Project#03/fortran/els.x new file mode 100644 index 0000000000000000000000000000000000000000..d9fa0d5e4fc1f5fd3495683576a27979bd51d66f GIT binary patch literal 53312 zcmeHw3w%`7wfC7sMS+OOQUTBK?NSQ2|%jgPBTZ*QsB+a_XLN^M0&^ZnP_d!IS;3c;`6 z?|X4z&fa_N_1bIgz0N-S>~qpyTE50?GHL3tXqRhL>X;}X#j>KKUuKXLYXw>|&hxc- zS^~;ehKc%Ok)T!_b>{HYF5woWM7K}YN2W6+o=TO5loDOMV{5XgQK^S z-(D~9RI2KAc`c$|i%2sk3%E*+bYz?E-J-sGZ+Nwek(lH zq`g$C>`6AE-wU!nGF>g$XeuRKIx7ClS3~)|cXKf+y-R>Kl`6U~f{yeY>!HlPPRfgC zmlkOkm6HAGSlm#*X?fn_hMMe#`lhz6*;@;iXD`poX>HC~%IzjM5b2dyZ_wscKhfvE z_dBWg9(*g^{M?Bjznt~@BcwO!K>P@Y4#GE@a~jH2FWMyxLNGdB@x0V1a%cs-lzTYVny`n9VXnwvc9t2Q-wL|yC}#nVlUTWdXD zx7SnE;J)2k?*pA)+v+2DjRE3qYx31MdfXnbx7lleOH6kSq=$o>TRcq$h%T_c$>-S& z!I3g`1k%Vr2nmcDDWbVGN*SF+bzPOWsv35Qk`mSqca<+(P<2CdYgjWpK6i7AufDmd 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0.181078653129682 + 9 8 9 2 0.044234528245132 + 9 9 8 3 -0.115242183476134 + 9 9 8 4 0.071369905102345 + 9 9 8 5 -0.071369905102345 + 9 8 9 3 -0.029743802645650 + 9 8 9 4 -0.023364154750318 + 9 8 9 5 0.023364154750318 + 9 9 8 6 0.055912476950067 + 9 8 9 6 0.012847889010515 + 9 9 8 7 0.055912476950067 + 9 8 9 7 0.012847889010515 + 9 9 8 8 0.296353939081570 + 9 8 9 8 0.015770501299918 + 9 9 9 1 0.031703797879678 + 9 9 9 2 0.304981529941436 + 9 9 9 3 -0.206879432071914 + 9 9 9 4 -0.206879432071914 + 9 9 9 5 0.206879432071914 + 9 9 9 6 0.085276746780538 + 9 9 9 7 0.085276746780538 + 9 9 9 8 0.085276746780538 + 9 9 9 9 0.774605895725855 diff --git a/Project#03/fortran/geom.dat b/Project#03/fortran/geom.dat new file mode 100644 index 0000000..9c536a9 --- /dev/null +++ b/Project#03/fortran/geom.dat @@ -0,0 +1,6 @@ +5 +6.000000000000 -0.000000000000 0.000000000000 0.000000000000 +1.000000000000 1.183771681898 -1.183771681898 -1.183771681898 +1.000000000000 1.183771681898 1.183771681898 1.183771681898 +1.000000000000 -1.183771681898 1.183771681898 -1.183771681898 +1.000000000000 -1.183771681898 -1.183771681898 1.183771681898 diff --git a/Project#03/fortran/geom_utils.f90 b/Project#03/fortran/geom_utils.f90 new file mode 100644 index 0000000..a23dfe6 --- /dev/null +++ b/Project#03/fortran/geom_utils.f90 @@ -0,0 +1,43 @@ +module geom_utils + use const + + implicit none + + contains + subroutine get_bond_lengths(natoms, coords, bondlengths) + integer, intent(in) :: natoms + real(p), intent(in) :: coords(:,:) + real(p), allocatable, intent(out) :: bondlengths(:,:) + + integer :: i, j, nelements + + ! Negligible memeory cost to store the full matrix rather than the lower triangular + nelements = natoms*(natoms-1)/2 + allocate(bondlengths(natoms, natoms), source=0.0_p) + + do i = 1, natoms-1 + do j = i+1, natoms + ! Diagonals set to 0.0 in allocation + bondlengths(j, i) = norm2(coords(:,i)-coords(:,j)) + bondlengths(i, j) = bondlengths(j, i) + end do + end do + end subroutine get_bond_lengths + + subroutine get_bond_angles(natoms, coords, bondlengths, angles) + integer, intent(in) :: natoms + real(p), intent(in) :: coords(:,:), bondlengths(:,:) + real(p), allocatable, intent(out) :: angles(:,:,:) + real(p), allocatable :: uvecs(3,:,:) + + allocate(uvecs(natoms, natoms), source=0.0_p) + do i = 1, natoms-1 + do j = i+1, natoms + ! Diagonals set to 0.0 in allocation + ! Column major - for efficient memory access use this ordering + uvec(:,j,i) + end do + end do + + +end module geom_utils diff --git a/Project#03/fortran/input.dat b/Project#03/fortran/input.dat new file mode 100644 index 0000000..6dfb483 --- /dev/null +++ b/Project#03/fortran/input.dat @@ -0,0 +1,43 @@ +psi: ( + label = "CH4 SCF Test Case" + wfn = scf + jobtype = oeprop + reference = rhf + basis = "STO-3G" + units = angstrom + subgroup = c1 + delete_tei = false + delete_oei = false + zmat = ( + C + H 1 r + H 1 r 2 td + H 1 r 2 td 3 d + H 1 r 2 td 4 d + ) + zvars = ( + r 1.085 + td 109.47122063449069136958 + d 120.0 + ) +) + +basis: ( + carbon: "STO-3G" = + ( (S ( 71.61683730 0.15432900) + ( 13.04509630 0.53532810) + ( 3.53051220 0.44463450) ) + (S ( 2.94124940 -0.09996720) + ( 0.68348310 0.39951280) + ( 0.22228990 0.70011550) ) + (P ( 2.94124940 0.15591630) + ( 0.68348310 0.60768370) + ( 0.22228990 0.39195740) ) + ) + + hydrogen: "STO-3G"= + ( (S ( 3.42525090 0.15432890) + ( 0.62391370 0.53532810) + ( 0.16885540 0.44463450) ) + ) +) diff --git a/Project#03/fortran/main.F90 b/Project#03/fortran/main.F90 new file mode 100644 index 0000000..2eb58ff --- /dev/null +++ b/Project#03/fortran/main.F90 @@ -0,0 +1,22 @@ +program main + + use const + use read_in_integrals + use system + + implicit none + + type(int_store_t) :: int_store + type(system_t) :: sys + integer :: i, iunit + + ! write to stdout + iunit = 6 + + write(iunit, *) 'Electronic Structure Programme' + + call read_integrals_in(sys, int_store) + call print_int_info(sys, int_store) + +end program main + diff --git a/Project#03/fortran/mux.dat b/Project#03/fortran/mux.dat new file mode 100644 index 0000000..9dca8dd --- /dev/null +++ b/Project#03/fortran/mux.dat @@ -0,0 +1,45 @@ + 1 1 0.000000000000000 + 2 1 0.000000000000000 + 2 2 0.000000000000000 + 3 1 -0.071855488532817 + 3 2 -0.838743574800986 + 3 3 0.000000000000000 + 4 1 -0.000000000000000 + 4 2 0.000000000000000 + 4 3 -0.000000000000000 + 4 4 0.000000000000000 + 5 1 0.000000000000000 + 5 2 0.000000000000000 + 5 3 -0.000000000000000 + 5 4 0.000000000000000 + 5 5 0.000000000000000 + 6 1 -0.004780775261548 + 6 2 -0.306592476518555 + 6 3 -0.519567036508228 + 6 4 0.163831354490276 + 6 5 0.163831354490276 + 6 6 -1.183771681897730 + 7 1 -0.004780775261548 + 7 2 -0.306592476518555 + 7 3 -0.519567036508228 + 7 4 -0.163831354490276 + 7 5 -0.163831354490276 + 7 6 -0.202918556316052 + 7 7 -1.183771681897730 + 8 1 0.004780775261548 + 8 2 0.306592476518555 + 8 3 -0.519567036508228 + 8 4 0.163831354490276 + 8 5 -0.163831354490276 + 8 6 -0.000000000000000 + 8 7 -0.000000000000000 + 8 8 1.183771681897730 + 9 1 0.004780775261548 + 9 2 0.306592476518555 + 9 3 -0.519567036508228 + 9 4 -0.163831354490276 + 9 5 0.163831354490276 + 9 6 0.000000000000000 + 9 7 0.000000000000000 + 9 8 0.202918556316052 + 9 9 1.183771681897731 diff --git a/Project#03/fortran/muy.dat b/Project#03/fortran/muy.dat new file mode 100644 index 0000000..3b70d58 --- /dev/null +++ b/Project#03/fortran/muy.dat @@ -0,0 +1,45 @@ + 1 1 -0.000000000000000 + 2 1 -0.000000000000000 + 2 2 -0.000000000000000 + 3 1 -0.000000000000000 + 3 2 0.000000000000000 + 3 3 -0.000000000000000 + 4 1 -0.071855488532817 + 4 2 -0.838743574800986 + 4 3 0.000000000000000 + 4 4 -0.000000000000000 + 5 1 -0.000000000000000 + 5 2 -0.000000000000000 + 5 3 0.000000000000000 + 5 4 -0.000000000000000 + 5 5 -0.000000000000000 + 6 1 0.004780775261548 + 6 2 0.306592476518555 + 6 3 0.163831354490276 + 6 4 -0.519567036508228 + 6 5 -0.163831354490276 + 6 6 1.183771681897730 + 7 1 -0.004780775261548 + 7 2 -0.306592476518555 + 7 3 -0.163831354490276 + 7 4 -0.519567036508228 + 7 5 -0.163831354490276 + 7 6 -0.000000000000000 + 7 7 -1.183771681897730 + 8 1 -0.004780775261548 + 8 2 -0.306592476518555 + 8 3 0.163831354490276 + 8 4 -0.519567036508228 + 8 5 0.163831354490276 + 8 6 -0.000000000000000 + 8 7 -0.202918556316052 + 8 8 -1.183771681897730 + 9 1 0.004780775261548 + 9 2 0.306592476518555 + 9 3 -0.163831354490276 + 9 4 -0.519567036508228 + 9 5 0.163831354490276 + 9 6 0.202918556316052 + 9 7 0.000000000000000 + 9 8 0.000000000000000 + 9 9 1.183771681897731 diff --git a/Project#03/fortran/muz.dat b/Project#03/fortran/muz.dat new file mode 100644 index 0000000..5e85ca2 --- /dev/null +++ b/Project#03/fortran/muz.dat @@ -0,0 +1,45 @@ + 1 1 -0.000000000000000 + 2 1 -0.000000000000000 + 2 2 -0.000000000000000 + 3 1 -0.000000000000000 + 3 2 0.000000000000000 + 3 3 -0.000000000000000 + 4 1 0.000000000000000 + 4 2 -0.000000000000000 + 4 3 0.000000000000000 + 4 4 -0.000000000000000 + 5 1 -0.071855488532817 + 5 2 -0.838743574800986 + 5 3 0.000000000000000 + 5 4 -0.000000000000000 + 5 5 -0.000000000000000 + 6 1 0.004780775261548 + 6 2 0.306592476518555 + 6 3 0.163831354490276 + 6 4 -0.163831354490276 + 6 5 -0.519567036508228 + 6 6 1.183771681897730 + 7 1 -0.004780775261548 + 7 2 -0.306592476518555 + 7 3 -0.163831354490276 + 7 4 -0.163831354490276 + 7 5 -0.519567036508228 + 7 6 0.000000000000000 + 7 7 -1.183771681897730 + 8 1 0.004780775261548 + 8 2 0.306592476518555 + 8 3 -0.163831354490276 + 8 4 0.163831354490276 + 8 5 -0.519567036508228 + 8 6 0.202918556316052 + 8 7 0.000000000000000 + 8 8 1.183771681897730 + 9 1 -0.004780775261548 + 9 2 -0.306592476518554 + 9 3 0.163831354490276 + 9 4 0.163831354490276 + 9 5 -0.519567036508228 + 9 6 0.000000000000000 + 9 7 -0.202918556316052 + 9 8 0.000000000000000 + 9 9 -1.183771681897729 diff --git a/Project#03/fortran/parallel.F90 b/Project#03/fortran/parallel.F90 new file mode 100644 index 0000000..f8451e3 --- /dev/null +++ b/Project#03/fortran/parallel.F90 @@ -0,0 +1,19 @@ +module parallel + #ifdef PARALLEL + use mpi_f08 + #endif + + use const + + implicit none + + ! MPI-related constants + integer :: iproc, nprocs + integer, parameter :: root = 0 + logical :: parent + + ! MPI communicators + integer :: inter_node_comm, intra_node_comm + + ! OpenMP thread count + integer :: nthreads diff --git a/Project#03/fortran/read_in_integrals.f90 b/Project#03/fortran/read_in_integrals.f90 new file mode 100644 index 0000000..61a836b --- /dev/null +++ b/Project#03/fortran/read_in_integrals.f90 @@ -0,0 +1,199 @@ +module read_in_integrals + use const + + implicit none + + type int_store_t + real(p) :: e_nuc = 0.0_p + real(p), allocatable :: ovlp(:,:) + real(p), allocatable :: ke(:,:) + real(p), allocatable :: ele_nuc(:,:) + real(p), allocatable :: core_hamil(:,:) + ! Too big, we compress with symmetry + real(p), allocatable :: eri(:) + end type int_store_t + + contains + subroutine read_integrals_in(sys, int_store) + ! Read in integral data supplied in separate files + use, intrinsic :: iso_fortran_env, only: iostat_end + use system + + type(int_store_t), intent(inout) :: int_store + type(system_t), intent(inout) :: sys + + character(10) :: enuc_f, ovlp_f, ke_f, ele_nuc_f, eri_f + integer :: i, j, iunit, ir, natoms, ios, nbasis, ibasis, jbasis, abasis, bbasis + real(p) :: intgrl + + ! stdout unit is 6 + iunit = 6 + + ! I/O status + ios = 0 + + nbasis = 0 + + ! Hard-coded filenames + enuc_f = 'enuc.dat' + ovlp_f = 's.dat' + ke_f = 't.dat' + ele_nuc_f = 'v.dat' + eri_f = 'eri.dat' + + !########### Nuclear repulsion ############ + write(iunit, *) 'Reading nuclear repulsion...' + open(newunit=ir, file=enuc_f, status='old', form='formatted') + read(ir, *) int_store%e_nuc + close(ir) + + !########### Get basis info ############### + write(iunit, *) 'Getting number of basis functions...' + open(newunit=ir, file=ovlp_f, status='old', form='formatted') + ! Pass through the file once to find nbasis first + do + read(ir, *, iostat=ios) ibasis, jbasis, intgrl + ! If EOF reached + if (ios==iostat_end) exit + if (ibasis>nbasis .or. jbasis>nbasis) then + nbasis = max(ibasis, jbasis) + end if + end do + + sys%nbasis = nbasis + + write(iunit, *) 'Allocating integral store...' + call init_int_store(sys, int_store) + + close(ir) + + !############# Overlap matrix ################## + write(iunit, *) 'Reading overlap matrix...' + open(newunit=ir, file=ovlp_f, status='old', form='formatted') + + do + read(ir, *, iostat=ios) ibasis, jbasis, intgrl + ! If EOF reached + if (ios==iostat_end) exit + ! Simple permutational symmetry + int_store%ovlp(ibasis,jbasis) = intgrl + int_store%ovlp(jbasis,ibasis) = intgrl + end do + close(ir) + + !############ Kinetic energy ############## + write(iunit, *) 'Reading kinetic integrals...' + open(newunit=ir, file=ke_f, status='old', form='formatted') + + do + read(ir, *, iostat=ios) ibasis, jbasis, intgrl + ! If EOF reached + if (ios==iostat_end) exit + ! Simple permutational symmetry + int_store%ke(ibasis,jbasis) = intgrl + int_store%ke(jbasis,ibasis) = intgrl + end do + close(ir) + + !########### Nuclear-electron integral ###### + write(iunit, *) 'Reading nuclear-electron integrals...' + open(newunit=ir, file=ele_nuc_f, status='old', form='formatted') + + do + read(ir, *, iostat=ios) ibasis, jbasis, intgrl + ! If EOF reached + if (ios==iostat_end) exit + ! Simple permutational symmetry + int_store%ele_nuc(ibasis,jbasis) = intgrl + int_store%ele_nuc(jbasis,ibasis) = intgrl + end do + close(ir) + + !######### Core Hamiltonian ############## + write(iunit, *) 'Constructing core Hamiltonian...' + int_store%core_hamil = int_store%ke + int_store%ele_nuc + + !######### ERI / Two-body integrals ######## + write(iunit, *) 'Reading two-body integrals' + open(newunit=ir, file=eri_f, status='old', form='formatted') + + do + read(ir, *, iostat=ios) ibasis, jbasis, abasis, bbasis, intgrl + ! If EOF reached + if (ios==iostat_end) exit + ! 8-fold permutational symmetry, we use compression to save space + int_store%eri(eri_ind(ibasis, jbasis, abasis, bbasis)) = intgrl + end do + close(ir) + + write(iunit, *) 'Done reading integrals!' + + end subroutine read_integrals_in + + subroutine init_int_store(sys, int_store) + use system + + type(system_t), intent(in) :: sys + type(int_store_t), intent(inout) :: int_store + + integer :: neri + + neri = sys%nbasis*(sys%nbasis-1)/2 + sys%nbasis + neri = neri*(neri-1)/2 + neri + + associate(nb=>sys%nbasis, is=>int_store) + allocate(is%ovlp(nb,nb), source=0.0_p) + allocate(is%ke(nb,nb), source=0.0_p) + allocate(is%ele_nuc(nb,nb), source=0.0_p) + allocate(is%core_hamil(nb,nb), source=0.0_p) + allocate(is%eri(neri), source=0.0_p) + end associate + end subroutine init_int_store + + elemental function eri_ind(i, j, a, b) result(ind) + integer, intent(in) :: i, j, a, b + integer :: ind + + integer :: ij, ab + + if (i >= j) then + ij = i*(i-1)/2 + j + else + ij = j*(j-1)/2 + i + end if + + if (a >= b) then + ab = a*(a-1)/2 + b + else + ab = b*(b-1)/2 + a + end if + + if (ij >= ab) then + ind = ij*(ij-1)/2 + ab + else + ind = ab*(ab-1)/2 + ij + end if + end function eri_ind + + subroutine print_int_info(sys, int_store) + use system + + type(system_t), intent(in) :: sys + type(int_store_t), intent(in) :: int_store + + integer :: iunit = 6 + integer :: i + + write(iunit, '(1X, 64("="))') + write(iunit, '(1X, A)') 'Integral information' + write(iunit, '(1X, 64("="))') + write(iunit, '(1X, A, 1X, I0)') 'Number of basis functions:', sys%nbasis + write(iunit, '(1X, A, 1X, ES15.8)') 'E_nuc:', int_store%e_nuc + + write(iunit, *) 'Two-electron integrals' + do i = 1, size(int_store%eri) + write(iunit, '(1X, I0, 1X, ES15.8)') i, int_store%eri(i) + end do + end subroutine print_int_info + +end module read_in_integrals diff --git a/Project#03/fortran/s.dat b/Project#03/fortran/s.dat new file mode 100644 index 0000000..cfa1ff6 --- /dev/null +++ b/Project#03/fortran/s.dat @@ -0,0 +1,45 @@ + 1 1 1.000000000000000 + 2 1 0.248362397956661 + 2 2 1.000000000000000 + 3 1 0.000000000000000 + 3 2 0.000000000000000 + 3 3 0.999999999999999 + 4 1 -0.000000000000000 + 4 2 0.000000000000000 + 4 3 0.000000000000000 + 4 4 0.999999999999999 + 5 1 0.000000000000000 + 5 2 0.000000000000000 + 5 3 0.000000000000000 + 5 4 0.000000000000000 + 5 5 0.999999999999999 + 6 1 0.063006775327623 + 6 2 0.493634843691260 + 6 3 0.270769041240711 + 6 4 -0.270769041240711 + 6 5 -0.270769041240711 + 6 6 1.000000000000000 + 7 1 0.063006775327623 + 7 2 0.493634843691260 + 7 3 0.270769041240711 + 7 4 0.270769041240711 + 7 5 0.270769041240711 + 7 6 0.171416971210824 + 7 7 1.000000000000000 + 8 1 0.063006775327623 + 8 2 0.493634843691261 + 8 3 -0.270769041240711 + 8 4 0.270769041240711 + 8 5 -0.270769041240711 + 8 6 0.171416971210824 + 8 7 0.171416971210824 + 8 8 1.000000000000000 + 9 1 0.063006775327623 + 9 2 0.493634843691260 + 9 3 -0.270769041240711 + 9 4 -0.270769041240711 + 9 5 0.270769041240711 + 9 6 0.171416971210824 + 9 7 0.171416971210824 + 9 8 0.171416971210824 + 9 9 1.000000000000000 diff --git a/Project#03/fortran/system.f90 b/Project#03/fortran/system.f90 new file mode 100644 index 0000000..c68bec3 --- /dev/null +++ b/Project#03/fortran/system.f90 @@ -0,0 +1,10 @@ +module system + use const + + implicit none + + type system_t + integer :: nbasis = 0 + end type system_t + +end module system \ No newline at end of file diff --git a/Project#03/fortran/t.dat b/Project#03/fortran/t.dat new file mode 100644 index 0000000..328ae64 --- /dev/null +++ b/Project#03/fortran/t.dat @@ -0,0 +1,45 @@ + 1 1 15.891123645988891 + 2 1 -0.085889884750479 + 2 2 0.472249956863652 + 3 1 -0.000000000000000 + 3 2 0.000000000000000 + 3 3 1.477728140458955 + 4 1 0.000000000000000 + 4 2 0.000000000000000 + 4 3 0.000000000000000 + 4 4 1.477728140458955 + 5 1 -0.000000000000000 + 5 2 -0.000000000000000 + 5 3 0.000000000000000 + 5 4 0.000000000000000 + 5 5 1.477728140458955 + 6 1 -0.010344430032030 + 6 2 0.108500715331350 + 6 3 0.152571116134591 + 6 4 -0.152571116134591 + 6 5 -0.152571116134591 + 6 6 0.760031756150991 + 7 1 -0.010344430032030 + 7 2 0.108500715331350 + 7 3 0.152571116134591 + 7 4 0.152571116134591 + 7 5 0.152571116134591 + 7 6 -0.005308006385401 + 7 7 0.760031756150991 + 8 1 -0.010344430032030 + 8 2 0.108500715331350 + 8 3 -0.152571116134591 + 8 4 0.152571116134591 + 8 5 -0.152571116134591 + 8 6 -0.005308006385401 + 8 7 -0.005308006385401 + 8 8 0.760031756150991 + 9 1 -0.010344430032030 + 9 2 0.108500715331350 + 9 3 -0.152571116134591 + 9 4 -0.152571116134591 + 9 5 0.152571116134590 + 9 6 -0.005308006385401 + 9 7 -0.005308006385401 + 9 8 -0.005308006385401 + 9 9 0.760031756150991 diff --git a/Project#03/fortran/v.dat b/Project#03/fortran/v.dat new file mode 100644 index 0000000..76b367c --- /dev/null +++ b/Project#03/fortran/v.dat @@ -0,0 +1,45 @@ + 1 1 -35.603626980402581 + 2 1 -4.676755261049649 + 2 2 -7.084529072583363 + 3 1 0.000000000000000 + 3 2 -0.000000000000000 + 3 3 -7.042708592061365 + 4 1 -0.000000000000000 + 4 2 0.000000000000000 + 4 3 -0.000000000000000 + 4 4 -7.042708592061365 + 5 1 0.000000000000000 + 5 2 0.000000000000000 + 5 3 -0.000000000000000 + 5 4 0.000000000000000 + 5 5 -7.042708592061365 + 6 1 -1.207710997119606 + 6 2 -2.981540218150075 + 6 3 -1.511693653842257 + 6 4 1.511693653842256 + 6 5 1.511693653842257 + 6 6 -4.983518228353068 + 7 1 -1.207710997119606 + 7 2 -2.981540218150075 + 7 3 -1.511693653842256 + 7 4 -1.511693653842256 + 7 5 -1.511693653842256 + 7 6 -0.934142211713616 + 7 7 -4.983518228353068 + 8 1 -1.207710997119606 + 8 2 -2.981540218150075 + 8 3 1.511693653842256 + 8 4 -1.511693653842257 + 8 5 1.511693653842257 + 8 6 -0.934142211713617 + 8 7 -0.934142211713616 + 8 8 -4.983518228353068 + 9 1 -1.207710997119606 + 9 2 -2.981540218150075 + 9 3 1.511693653842257 + 9 4 1.511693653842257 + 9 5 -1.511693653842255 + 9 6 -0.934142211713616 + 9 7 -0.934142211713615 + 9 8 -0.934142211713616 + 9 9 -4.983518228353067 From cbd22974668ccea644529e761b67d1f7b30a460d Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Tue, 14 Dec 2021 21:58:00 +0000 Subject: [PATCH 02/71] Working CMake and BLAS, starting on HF --- .gitignore | 1 + Project#03/fortran/CMakeLists.txt | 23 +++++++ Project#03/fortran/{Makefile => Makefile.old} | 0 Project#03/fortran/els.x | Bin 53312 -> 455768 bytes Project#03/fortran/geom_utils.f90 | 43 ------------- Project#03/fortran/parallel.F90 | 19 ------ Project#03/fortran/{ => src}/const.F90 | 0 Project#03/fortran/src/error_handling.f90 | 21 +++++++ Project#03/fortran/src/hf.f90 | 57 ++++++++++++++++++ Project#03/fortran/src/linalg.f90 | 35 +++++++++++ Project#03/fortran/{ => src}/main.F90 | 3 + .../fortran/{ => src}/read_in_integrals.f90 | 4 -- Project#03/fortran/{ => src}/system.f90 | 0 13 files changed, 140 insertions(+), 66 deletions(-) create mode 100644 Project#03/fortran/CMakeLists.txt rename Project#03/fortran/{Makefile => Makefile.old} (100%) delete mode 100644 Project#03/fortran/geom_utils.f90 delete mode 100644 Project#03/fortran/parallel.F90 rename Project#03/fortran/{ => src}/const.F90 (100%) create mode 100644 Project#03/fortran/src/error_handling.f90 create mode 100644 Project#03/fortran/src/hf.f90 create mode 100644 Project#03/fortran/src/linalg.f90 rename Project#03/fortran/{ => src}/main.F90 (87%) rename Project#03/fortran/{ => src}/read_in_integrals.f90 (97%) rename Project#03/fortran/{ => src}/system.f90 (100%) diff --git a/.gitignore b/.gitignore index aea4939..9a63ab9 100644 --- a/.gitignore +++ b/.gitignore @@ -2,3 +2,4 @@ *sublime* *.mod *.o +build/ diff --git a/Project#03/fortran/CMakeLists.txt b/Project#03/fortran/CMakeLists.txt new file mode 100644 index 0000000..4bc497e --- /dev/null +++ b/Project#03/fortran/CMakeLists.txt @@ -0,0 +1,23 @@ +# References: +# https://gitlab.kitware.com/cmake/community/-/wikis/doc/cmake/languages/fortran/ForFortranExample +# https://fortranwiki.org/fortran/show/Build+tools + +cmake_minimum_required (VERSION 3.12) +project (els) +enable_language (Fortran) + +if (CMAKE_Fortran_COMPILER_ID MATCHES "GNU") + set (dialect "-ffree-form -std=f2008 -fimplicit-none") + set (extras "-fcheck=all -ggdb") +endif () +if (CMAKE_Fortran_COMPILER_ID MATCHES "Intel") + set (dialect "-stand f08 -free -implicitnone") + set (extras "-check bounds") +endif () + +set (CMAKE_Fortran_FLAGS_DEBUG "${CMAKE_Fortran_FLAGS_DEBUG} ${extras}") +set (CMAKE_Fortran_FLAGS "${CMAKE_Fortran_FLAGS} ${dialect}") + +file (GLOB_RECURSE sources src/*.f90 src/*.F90) +add_executable(els.x ${sources}) +target_link_libraries (els.x /opt/OpenBLAS/lib/libopenblas.a -lpthread) diff --git a/Project#03/fortran/Makefile b/Project#03/fortran/Makefile.old similarity index 100% rename from Project#03/fortran/Makefile rename to Project#03/fortran/Makefile.old diff --git a/Project#03/fortran/els.x b/Project#03/fortran/els.x index 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z1ueB-(W`alUP-?db;iSKEFk|!{HX6LdbJ*%5tN9s{i=T}y;VQx0h&?1TDQ*lnxH=} z*{DR(tMo%u80ocMiPf=w9KShRkDgB+jqGqzBKS|6DhtrU!tQqx$k{bb6 z^z@do@lfnknk?y!IF!F!%HJPRq39HNdK~&cO8Sp!f!uIJ(q9mVeuxG(j#UvIK9W8! z4*f-s3;Ln6$S;=kk@idbzMx;P0drrAGzE7a|BEirW7G78aC_ diff --git a/Project#03/fortran/geom_utils.f90 b/Project#03/fortran/geom_utils.f90 deleted file mode 100644 index a23dfe6..0000000 --- a/Project#03/fortran/geom_utils.f90 +++ /dev/null @@ -1,43 +0,0 @@ -module geom_utils - use const - - implicit none - - contains - subroutine get_bond_lengths(natoms, coords, bondlengths) - integer, intent(in) :: natoms - real(p), intent(in) :: coords(:,:) - real(p), allocatable, intent(out) :: bondlengths(:,:) - - integer :: i, j, nelements - - ! Negligible memeory cost to store the full matrix rather than the lower triangular - nelements = natoms*(natoms-1)/2 - allocate(bondlengths(natoms, natoms), source=0.0_p) - - do i = 1, natoms-1 - do j = i+1, natoms - ! Diagonals set to 0.0 in allocation - bondlengths(j, i) = norm2(coords(:,i)-coords(:,j)) - bondlengths(i, j) = bondlengths(j, i) - end do - end do - end subroutine get_bond_lengths - - subroutine get_bond_angles(natoms, coords, bondlengths, angles) - integer, intent(in) :: natoms - real(p), intent(in) :: coords(:,:), bondlengths(:,:) - real(p), allocatable, intent(out) :: angles(:,:,:) - real(p), allocatable :: uvecs(3,:,:) - - allocate(uvecs(natoms, natoms), source=0.0_p) - do i = 1, natoms-1 - do j = i+1, natoms - ! Diagonals set to 0.0 in allocation - ! Column major - for efficient memory access use this ordering - uvec(:,j,i) - end do - end do - - -end module geom_utils diff --git a/Project#03/fortran/parallel.F90 b/Project#03/fortran/parallel.F90 deleted file mode 100644 index f8451e3..0000000 --- a/Project#03/fortran/parallel.F90 +++ /dev/null @@ -1,19 +0,0 @@ -module parallel - #ifdef PARALLEL - use mpi_f08 - #endif - - use const - - implicit none - - ! MPI-related constants - integer :: iproc, nprocs - integer, parameter :: root = 0 - logical :: parent - - ! MPI communicators - integer :: inter_node_comm, intra_node_comm - - ! OpenMP thread count - integer :: nthreads diff --git a/Project#03/fortran/const.F90 b/Project#03/fortran/src/const.F90 similarity index 100% rename from Project#03/fortran/const.F90 rename to Project#03/fortran/src/const.F90 diff --git a/Project#03/fortran/src/error_handling.f90 b/Project#03/fortran/src/error_handling.f90 new file mode 100644 index 0000000..4919d4c --- /dev/null +++ b/Project#03/fortran/src/error_handling.f90 @@ -0,0 +1,21 @@ +module error_handling + implicit none + + contains + subroutine error(procedure, error_msg) + use, intrinsic :: iso_fortran_env, only: error_unit, output_unit + + character(*), intent(in) :: procedure, error_msg + character(3), parameter :: error_str = '999' + + write(error_unit, '(1X, A6)') 'ERROR.' + write(error_unit, '(1X, A)') 'Programme stops in procedure: '//adjustl(procedure)//'.' + write(error_unit, '(1X, A)') 'Reason: '//adjustl(error_msg)//'.' + write(error_unit, '(1X, A10)') 'EXITING...' + + stop error_str + + return + end subroutine error + +end module error_handling diff --git a/Project#03/fortran/src/hf.f90 b/Project#03/fortran/src/hf.f90 new file mode 100644 index 0000000..2525a96 --- /dev/null +++ b/Project#03/fortran/src/hf.f90 @@ -0,0 +1,57 @@ +module hf + use const + + implicit none + + contains + subroutine do_hartree_fock(sys, int_store) + use error_handling + use system + use read_in_integrals + use linalg + + type(int_store_t), intent(in) :: int_store + type(system_t), intent(in) :: sys + + type(mat_t) :: ovlp + + call init_mat_t(sys, int_store%ovlp, ovlp) + + call orthogonalise(ovlp) + + print*, ovlp%W + end subroutine do_hartree_fock + + + subroutine orthogonalise(mat) + ! For a symmetric matrix A we produce + ! A = CLC^(-1) + ! With L and C stored in a mat_t data structure + + use linalg + use error_handling + + type(mat_t), intent(inout) :: mat + + integer :: ierr + + call eigs(mat, ierr) + if (ierr /= 0) call error('hf::orthogonalise', 'Orthogonalisation failed!') + end subroutine orthogonalise + + subroutine init_mat_t(sys, matrix, mat) + use read_in_integrals + use linalg + use system + + type(system_t), intent(in) :: sys + real(p), intent(in) :: matrix(:,:) + type(mat_t), intent(out) :: mat + + mat%N = sys%nbasis + allocate(mat%A(mat%N, mat%N)) + mat%A(:,:) = matrix(:,:) + allocate(mat%W(sys%nbasis)) + end subroutine init_mat_t + +end module hf diff --git a/Project#03/fortran/src/linalg.f90 b/Project#03/fortran/src/linalg.f90 new file mode 100644 index 0000000..e76127e --- /dev/null +++ b/Project#03/fortran/src/linalg.f90 @@ -0,0 +1,35 @@ +module linalg + use const + + implicit none + + type mat_t + ! A structure that holds the original matrix, the eigenvalues and the eigenvalue matrix + integer :: N = -1 ! Dimension + real(p), allocatable :: A(:,:) ! Original/eigenvector matrix + real(p), allocatable :: W(:) ! Eigenvalues + end type mat_t + + contains + subroutine eigs(mat, ierr) + ! Wrapper around LAPACK dsyev, so named to be reminiscent of the NumPy package + ! Finds the eigenvalues and eigenvectors of a double-precision symmetric matrix + ! This further automates finding the optimal workspace by first passing lwork = -1 + ! to LAPACK dsyev, where work(1) contains the optimised workspace dimension, + ! then we pass that to dsyev again for actual computation of eigen quantities + + type(mat_t), intent(inout) :: mat + integer, intent(out) :: ierr + + real(p), allocatable :: work(:) + integer :: lwork, i + + lwork = -1 + do i = 1, 2 + allocate(work(abs(lwork))) + call dsyev('V', 'U', mat%N, mat%A(:,:), mat%N, mat%W, work, lwork, ierr) + lwork = ceiling(work(1)) ! nint used in HANDE + deallocate(work) + end do + end subroutine eigs +end module linalg diff --git a/Project#03/fortran/main.F90 b/Project#03/fortran/src/main.F90 similarity index 87% rename from Project#03/fortran/main.F90 rename to Project#03/fortran/src/main.F90 index 2eb58ff..70cd164 100644 --- a/Project#03/fortran/main.F90 +++ b/Project#03/fortran/src/main.F90 @@ -3,6 +3,7 @@ program main use const use read_in_integrals use system + use hf implicit none @@ -17,6 +18,8 @@ program main call read_integrals_in(sys, int_store) call print_int_info(sys, int_store) + + call do_hartree_fock(sys, int_store) end program main diff --git a/Project#03/fortran/read_in_integrals.f90 b/Project#03/fortran/src/read_in_integrals.f90 similarity index 97% rename from Project#03/fortran/read_in_integrals.f90 rename to Project#03/fortran/src/read_in_integrals.f90 index 61a836b..b360475 100644 --- a/Project#03/fortran/read_in_integrals.f90 +++ b/Project#03/fortran/src/read_in_integrals.f90 @@ -190,10 +190,6 @@ subroutine print_int_info(sys, int_store) write(iunit, '(1X, A, 1X, I0)') 'Number of basis functions:', sys%nbasis write(iunit, '(1X, A, 1X, ES15.8)') 'E_nuc:', int_store%e_nuc - write(iunit, *) 'Two-electron integrals' - do i = 1, size(int_store%eri) - write(iunit, '(1X, I0, 1X, ES15.8)') i, int_store%eri(i) - end do end subroutine print_int_info end module read_in_integrals diff --git a/Project#03/fortran/system.f90 b/Project#03/fortran/src/system.f90 similarity index 100% rename from Project#03/fortran/system.f90 rename to Project#03/fortran/src/system.f90 From 8bdae7803f6bc32b6a98d24aa6c84d3e86d69c04 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 15 Dec 2021 14:47:53 +0000 Subject: [PATCH 03/71] Restructure directories --- .gitignore | 1 + .../fortran/CMakeLists.txt => CMakeLists.txt | 0 .../fortran/Makefile.old => Makefile.old | 0 Project#01/README.md | 130 - Project#01/eigen.tar.gz | Bin 562351 -> 0 bytes Project#01/figures/.DS_Store | Bin 8196 -> 0 bytes Project#01/figures/bond-angle.pdf | Bin 46172 -> 0 bytes Project#01/figures/bond-angle.png | Bin 5074 -> 0 bytes Project#01/figures/center-of-mass.pdf | Bin 37811 -> 0 bytes Project#01/figures/center-of-mass.png | Bin 12250 -> 0 bytes Project#01/figures/determinant.png | Bin 3847 -> 0 bytes Project#01/figures/distances.pdf | Bin 51889 -> 0 bytes Project#01/figures/distances.png | Bin 8113 -> 0 bytes Project#01/figures/distances2.png | Bin 8117 -> 0 bytes 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-3,3 +3,4 @@ *.mod *.o build/ +original_projects/ diff --git a/Project#03/fortran/CMakeLists.txt b/CMakeLists.txt similarity index 100% rename from Project#03/fortran/CMakeLists.txt rename to CMakeLists.txt diff --git a/Project#03/fortran/Makefile.old b/Makefile.old similarity index 100% rename from Project#03/fortran/Makefile.old rename to Makefile.old diff --git a/Project#01/README.md b/Project#01/README.md deleted file mode 100644 index b6a1d47..0000000 --- a/Project#01/README.md +++ /dev/null @@ -1,130 +0,0 @@ -# Molecular-Geometry-Analysis -The purpose of this project is to introduce you to fundamental C-language (or C++) programming techniques in the context of a scientific problem, viz. the calculation of the internal coordinates (bond lengths, bond angles, dihedral angles), moments of inertia, and rotational constants of a polyatomic molecule. A concise set of instructions for this project may be found [here](./project1-instructions.pdf). - -We thank Dr. Yukio Yamaguchi of the University of Georgia for the original version of this project. - -## Step 1: Read the Coordinate Data from Input -The input to the program is the set of Cartesian coordinates of the atoms (in bohr) and their associated atomic numbers. A sample molecule (acetaldehyde) to use as input to the program is: - - 7 - 6 0.000000000000 0.000000000000 0.000000000000 - 6 0.000000000000 0.000000000000 2.845112131228 - 8 1.899115961744 0.000000000000 4.139062527233 - 1 -1.894048308506 0.000000000000 3.747688672216 - 1 1.942500819960 0.000000000000 -0.701145981971 - 1 -1.007295466862 -1.669971842687 -0.705916966833 - 1 -1.007295466862 1.669971842687 -0.705916966833 - -The first line above is the number of atoms (an integer), while the remaining lines contain the z-values and x-, y-, and z-coordinates of each atom (one integer followed by three double-precision floating-point numbers). This [input file](./input/acetaldehyde.dat) ("acetaldehyde.dat") along with a few other test cases can be found in this repository in the [input directory](./input). - -After downloading the file to your computer (to a file called “geom.dat”, for example), you must open the file, read the data from each line into appropriate variables, and finally close the file. - -- [Hint #1](./hints/hint1-1.md): Opening and closing the file stream -- [Hint #2](./hints/hint1-2.md): Reading the number of atoms -- [Hint #3](./hints/hint1-3.md): Storing the z-values and the coordinates -- [Solution](./hints/step1-solution.md) - -## Step 2: Bond Lengths -Calculate the interatomic distances using the expression: - - - -where x, y, and z are Cartesian coordinates and i and j denote atomic indices. - -- [Hint 1](./hints/hint2-1.md): Memory allocation -- [Hint 2](./hints/hint2-2.md): Loop structure -- [Hint 3](./hints/hint2-3.md): Printing the results -- [Hint 4](./hints/hint2-4.md): Extending the Molecule class -- [Solution](./hints/step2-solution.md) - -## Step 3: Bond Angles -Calculate all possible bond angles. For example, the angle, φijk, between atoms i-j-k, where j is the central atom is given by: - - - -where the eij are unit vectors between the atoms, e.g., - - - -- [Hint 1](./hints/hint3-1.md): Memory allocation for the unit vectors -- [Hint 2](./hints/hint3-2.md): Avoiding a divide-by-zero -- [Hint 3](./hints/hint3-3.md): Memory allocation for the bond angles -- [Hint 4](./hints/hint3-4.md): Smart printing -- [Hint 5](./hints/hint3-5.md): Trigonometric functions -- [Solution](./hints/step3-solution.md) - -## Step 4: Out-of-Plane Angles -Calculate all possible out-of-plane angles. For example, the angle θijkl for atom i out of the plane containing atoms j-k-l (with k as the central atom, connected to i) is given by: - - - -- [Hint 1](./hints/hint4-1.md): Memory allocation? -- [Hint 2](./hints/hint4-2.md): Cross products -- [Hint 3](./hints/hint4-3.md): Numerical precision -- [Hint 4](./hints/hint4-4.md): Smarter printing -- [Solution](./hints/step4-solution.md) - -## Step 5: Torsion/Dihedral Angles -Calculate all possible torsional angles. For example, the torsional angle τijkl for the atom connectivity i-j-k-l is given by: - - - -Can you also determine the sign of the torsional angle? - -- [Hint 1](./hints/hint5-1.md): Memory allocation? -- [Hint 2](./hints/hint5-2.md): Numerical precision -- [Hint 3](./hints/hint5-3.md): Smart printing -- [Hint 4](./hints/hint5-4.md): Sign -- [Solution](./hints/step5-solution.md) - -## Step 6: Center-of-Mass Translation -Find the center of mass of the molecule: - - - -where mi is the mass of atom i and the summation runs over all atoms in the molecule. - -Translate the input coordinates of the molecule to the center-of-mass. - -- [Hint 1](./hints/hint6-1.md): Atomic masses -- [Hint 2](./hints/hint6-2.md): Translating between atomic number and atomic mass -- [Solution](./hints/step6-solution.md) - -## Step 7: Principal Moments of Inertia -Calculate elements of the [moment of inertia tensor](http://en.wikipedia.org/wiki/Moment_of_inertia_tensor). - -Diagonal: - - - -Off-diagonal (add a negative sign): - - - -Diagonalize the inertia tensor to obtain the principal moments of inertia: - - - -Report the moments of inertia in amu bohr2, amu Å2, and g cm2. - -Based on the relative values of the principal moments, determine the [molecular rotor type](http://en.wikipedia.org/wiki/Rotational_spectroscopy): linear, oblate, prolate, asymmetric. - -- [Hint 1](./hints/hint7-1.md): Diagonalization of a 3×3 matrix -- [Hint 2](./hints/hint7-2.md): Physical constants -- [Solution](./hints/step7-solution.md) - -## Step 8: Rotational Constants -Compute the rotational constants in cm-1 and MHz: - - - -- [Solution](./hints/step8-solution.md) - - -## Test Cases -- Acetaldehyde: [input coordinates](./input/acetaldehyde.dat) | [output](./output/acetaldehyde_out.txt) -- Benzene: [input coordinates](./input/benzene.dat) | [output](./output/benzene_out.txt) -- Allene: [input coordinates](./input/allene.dat) | [output](./output/allene_out.txt) - -## References -E.B. Wilson, J.C. Decius, and P.C. 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zXGnwifGK^N6>GfkHl+;@vIM;B0a}QdFsvMd^sUnrYidi$yyj#}ykG>&PVv-mSw-2^ zRm;UQzNrn0G?tZMS+*jz`V(utG#;jAnIgW}TDFXEJeuS6u31;xRPU`{TSuSB_2PQN zTdxbEUbjy1-rRWW>e@!{t!vhNxPHBNeeLSTdSXng4?c=(Ca^E=D&D$}uB~lqxCwde z8?CL87;~8E`>)n7&eqhJKGvH0&aU};y6G&IFZ>!`=9S;8P2=WYkOj%~aoBO+kF{o- zgOlxoKwNKljc?bAs{sCm-8366{1M_?@gZA(u-hAp;DJ{9kgdfU`hs!huM~Un+?0=h z2G`_Yt3m0en7u_GCeD&;D4|Oo)0czO+0#DDYcbo4Z!H@w%pVDP@#r}ofHfH^B5YA< zG#hGc>D;N$9;eF~buz5xeU9;`vwAm0BI7)k)*{pS4b`SEAE$HhOT!CX)|r~L`0{bO z0;34|0q6AW00lXNAJVxDCFw3mV`3MPN?BxESJbx&FdF8tL#C(&hkKN=?oc#PhW&uD zO|c+85g+smQtj%7(x|UpVR?8MyF)4SZ|jCW4x?e7gLeSXGwW%H7kS}8r;h|gs;4um zl(8U}Az9WQ0vZi$#hFG}Fojsn%K{x@OzrSPiNv@lA6&VFOrr!Jo?(Mc+Y-uk zvdCt5%X*rZmeCr)xLz#C|goX(=bkMIcydl=tdJ&aqPtJRBXzOZT&7 zk`K3Wfg7b`vdAyaBLB@G7r0*rK8yU-Lf-1X>K-m|r|ei3d1*623k&0XR7~x|BH$iS rtMD)5FUQ|J&@5F1MNxKsk^yDrMf^wGi<#uV+{@+ZW-jw#L6!dt*I#AI diff --git a/Project#01/fortran/geom.dat b/Project#01/fortran/geom.dat deleted file mode 100644 index e005b69..0000000 --- a/Project#01/fortran/geom.dat +++ /dev/null @@ -1,8 +0,0 @@ -7 -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 diff --git a/Project#01/fortran/geom_read_in.f90 b/Project#01/fortran/geom_read_in.f90 deleted file mode 100644 index 2cfdfd3..0000000 --- a/Project#01/fortran/geom_read_in.f90 +++ /dev/null @@ -1,36 +0,0 @@ -module geom_read_in - use const - - implicit none - - contains - - subroutine read_geometry_in(geom_filename, charges, coords) - ! Read in geometry data supplied in a file - character(10), intent(in) :: geom_filename - integer, allocatable, intent(out) :: charges(:) - real(p), allocatable, intent(out) :: coords(:,:) - - integer :: i, iunit, ir, natoms - - ! stdout unit is 6 - iunit = 6 - - ! newunit chooses an unused file handle, 'old' means existing file - open(newunit=ir, file=geom_filename, status='old', form='formatted') - read(ir, *) natoms - - ! Lazy allocation! - ! [TODO] make check_allocate subroutine - allocate(charges(natoms)) - allocate(coords(3,natoms)) - - do i = 1, natoms - read(ir, *) charges(i), coords(:,i) - end do - - close(ir) - - end subroutine read_geometry_in - -end module geom_read_in diff --git a/Project#01/fortran/geom_utils.f90 b/Project#01/fortran/geom_utils.f90 deleted file mode 100644 index a23dfe6..0000000 --- a/Project#01/fortran/geom_utils.f90 +++ /dev/null @@ -1,43 +0,0 @@ -module geom_utils - use const - - implicit none - - contains - subroutine get_bond_lengths(natoms, coords, bondlengths) - integer, intent(in) :: natoms - real(p), intent(in) :: coords(:,:) - real(p), allocatable, intent(out) :: bondlengths(:,:) - - integer :: i, j, nelements - - ! Negligible memeory cost to store the full matrix rather than the lower triangular - nelements = natoms*(natoms-1)/2 - allocate(bondlengths(natoms, natoms), source=0.0_p) - - do i = 1, natoms-1 - do j = i+1, natoms - ! Diagonals set to 0.0 in allocation - bondlengths(j, i) = norm2(coords(:,i)-coords(:,j)) - bondlengths(i, j) = bondlengths(j, i) - end do - end do - end subroutine get_bond_lengths - - subroutine get_bond_angles(natoms, coords, bondlengths, angles) - integer, intent(in) :: natoms - real(p), intent(in) :: coords(:,:), bondlengths(:,:) - real(p), allocatable, intent(out) :: angles(:,:,:) - real(p), allocatable :: uvecs(3,:,:) - - allocate(uvecs(natoms, natoms), source=0.0_p) - do i = 1, natoms-1 - do j = i+1, natoms - ! Diagonals set to 0.0 in allocation - ! Column major - for efficient memory access use this ordering - uvec(:,j,i) - end do - end do - - -end module geom_utils diff --git a/Project#01/fortran/main.F90 b/Project#01/fortran/main.F90 deleted file mode 100644 index a8e8766..0000000 --- a/Project#01/fortran/main.F90 +++ /dev/null @@ -1,36 +0,0 @@ -program main - - use const - use geom_read_in - use geom_utils - - implicit none - - integer :: i, iunit - character(20) :: geometry_filename - integer, allocatable :: charges(:) - real(p), allocatable :: coords(:,:), bondlengths(:,:) - - ! write to stdout - iunit = 6 - - write(iunit, *) 'Electronic Structure Programme' - - geometry_filename = 'geom.dat' - - call read_geometry_in(geometry_filename, charges, coords) - - write(iunit, *) 'The geometry is as follows' - do i = 1, size(charges) - write(iunit, *) charges(i), coords(:,i) - end do - - call get_bond_lengths(size(charges), coords, bondlengths) - - write(iunit, *) 'The interatomic distances are as follows' - do i = 1, size(charges) - write(iunit, *) bondlengths(:,i) - end do - -end program main - diff --git a/Project#01/fortran/parallel.F90 b/Project#01/fortran/parallel.F90 deleted file mode 100644 index f8451e3..0000000 --- a/Project#01/fortran/parallel.F90 +++ /dev/null @@ -1,19 +0,0 @@ -module parallel - #ifdef PARALLEL - use mpi_f08 - #endif - - use const - - implicit none - - ! MPI-related constants - integer :: iproc, nprocs - integer, parameter :: root = 0 - logical :: parent - - ! MPI communicators - integer :: inter_node_comm, intra_node_comm - - ! OpenMP thread count - integer :: nthreads diff --git a/Project#01/hints/hint1-1.md b/Project#01/hints/hint1-1.md deleted file mode 100644 index 7ae4d3b..0000000 --- a/Project#01/hints/hint1-1.md +++ /dev/null @@ -1,20 +0,0 @@ -To open a file named "geom.dat", you need a file stream object: - -```c++ -#include -#include -#include - -... - -int main() -{ - ifstream input("geom.dat"); - - ... - - input.close(); - - return 0; -} -``` diff --git a/Project#01/hints/hint1-2.md b/Project#01/hints/hint1-2.md deleted file mode 100644 index 7fa15f6..0000000 --- a/Project#01/hints/hint1-2.md +++ /dev/null @@ -1,21 +0,0 @@ -Use the ">>" operator to read the data from the file: - -```c++ -#include -#include -#include - -... - -int main() -{ - ifstream input("geom.dat"); - - int natom; - input >> natom; - - input.close(); - - return 0; -} -``` diff --git a/Project#01/hints/hint1-3.md b/Project#01/hints/hint1-3.md deleted file mode 100644 index ecd2d17..0000000 --- a/Project#01/hints/hint1-3.md +++ /dev/null @@ -1,20 +0,0 @@ -It may be convenient to use arrays to store the z-values and Cartesian coordinates of the atoms: -```c++ -int zval[50]; -double x[50], y[50], z[50]; -``` - -A more elegant solution is to allocate the memory dynamically for each array once you know the number of atoms: -```c++ -int natom; -input >> natom; - -int *zval = new int[natom]; -double *x = new double[natom]; -double *y = new double[natom]; -double *z = new double[natom]; - -delete[] zval; delete[] x; delete[] y; delete[] z; -``` - -Don't forget to delete[] the memory after you're finished! diff --git a/Project#01/hints/hint2-1.md b/Project#01/hints/hint2-1.md deleted file mode 100644 index 68bb23c..0000000 --- a/Project#01/hints/hint2-1.md +++ /dev/null @@ -1,18 +0,0 @@ -If we choose to store the matrix of bond distances, we need to allocate the necessary memory, either as a static two-dimensional array: -```c++ -double R[50][50]; -``` - -or via dynamic allocation using the [Molecule class](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Classes-and-Objects): -```c++ -double **R = new double* [mol.natom]; -for(int i=0; i < mol.natom; i++) - R[i] = new double[mol.natom]; -``` - -Don't forget to delete[] the memory at the end of the program: -```c++ -for(int i=0; i < mol.natom; i++) - delete[] R[i]; -delete[] R; -``` diff --git a/Project#01/hints/hint2-2.md b/Project#01/hints/hint2-2.md deleted file mode 100644 index 49dc043..0000000 --- a/Project#01/hints/hint2-2.md +++ /dev/null @@ -1,15 +0,0 @@ -To build the distance matrix, we need a loop for each index: -```c++ - ... - #include - ... - - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < mol.natom; j++) { - R[i][j] = sqrt( (mol.geom[i][0]-mol.geom[j][0])*(mol.geom[i][0]-mol.geom[j][0]) - + (mol.geom[i][1]-mol.geom[j][1])*(mol.geom[i][1]-mol.geom[j][1]) - + (mol.geom[i][2]-mol.geom[j][2])*(mol.geom[i][2]-mol.geom[j][2]) ); - } - } -``` -Note also that the `sqrt()` function is part of the C math library; thus we need the `#include ` directive. diff --git a/Project#01/hints/hint2-3.md b/Project#01/hints/hint2-3.md deleted file mode 100644 index 30bbb93..0000000 --- a/Project#01/hints/hint2-3.md +++ /dev/null @@ -1,7 +0,0 @@ -To print the interatomic distance matrix, we could just run through its unique values: -```c++ - for(int i=0; i < mol.natom; i++) - for(int j=0; j < i; j++) - printf("%d %d %8.5f\n", i, j, R[i][j]); -``` -Note the conditional on the index `j` which keeps the code form printing redundant information. diff --git a/Project#01/hints/hint2-4.md b/Project#01/hints/hint2-4.md deleted file mode 100644 index b7c4f47..0000000 --- a/Project#01/hints/hint2-4.md +++ /dev/null @@ -1,11 +0,0 @@ -Now that we've written some code to compute bond distances, we can extend the Molecule class a bit more to define our `bond()` function: -```c++ -double Molecule::bond(int a, int b) -{ - return sqrt( (geom[a][0]-geom[b][0])*(geom[a][0]-geom[b][0]) - + (geom[a][1]-geom[b][1])*(geom[a][1]-geom[b][1]) - + (geom[a][2]-geom[b][2])*(geom[a][2]-geom[b][2]) ); -} -``` - -Note that since `bond()` is a member function of the Molecule class, we can access the geom array with just `geom` rather than `mol.geom` diff --git a/Project#01/hints/hint3-1.md b/Project#01/hints/hint3-1.md deleted file mode 100644 index 8bc992a..0000000 --- a/Project#01/hints/hint3-1.md +++ /dev/null @@ -1,18 +0,0 @@ -Each unit vector points from one atom to another, hence each Cartesian component should be treated as a matrix, much like the interatomic distance matrix. For now, let's store the unit vectors in memory, but later we'll write a function to recompute them as needed: -```c++ - double **ex = new double* [mol.natom]; - double **ey = new double* [mol.natom]; - double **ez = new double* [mol.natom]; - for(int i=0; i < mol.natom; i++) { - ex[i] = new double[mol.natom]; - ey[i] = new double[mol.natom]; - ez[i] = new double[mol.natom]; - } -``` -And don't forget to delete[] them at the end: -```c++ - for(int i=0; i < mol.natom; i++) { - delete[] ex[i]; delete[] ey[i]; delete[] ez[i]; - } - delete[] ex; delete[] ey; delete[] ez; -``` diff --git a/Project#01/hints/hint3-2.md b/Project#01/hints/hint3-2.md deleted file mode 100644 index 731dda4..0000000 --- a/Project#01/hints/hint3-2.md +++ /dev/null @@ -1,10 +0,0 @@ -Be careful about the diagonal elements of the unit vector matrices because of the division by the bond distance between atoms i and j. You should restrict the loops to skip those elements involving a divide-by-zero condition! -```c++ - for(i=0; i < mol.natom; i++) { - for(j=0; j < i; j++) { - ex[i][j] = ex[j][i] = -(x[i] - x[j])/R[i][j]; - ey[i][j] = ey[j][i] = -(y[i] - y[j])/R[i][j]; - ez[i][j] = ez[j][i] = -(z[i] - z[j])/R[i][j]; - } - } -``` diff --git a/Project#01/hints/hint3-3.md b/Project#01/hints/hint3-3.md deleted file mode 100644 index f6f19ee..0000000 --- a/Project#01/hints/hint3-3.md +++ /dev/null @@ -1,10 +0,0 @@ -If you choose to store the bond angles for later use (not absolutely necessary, as we'll see), you need a three-dimensional array: -```c++ - double ***phi = new double** [mol.natom]; - for(int i=0; i < mol.natom; i++) { - phi[i] = new double* [mol.natom]; - for(int j=0; j < mol.natom; j++) { - phi[i][j] = new double[mol.natom]; - } - } -``` diff --git a/Project#01/hints/hint3-4.md b/Project#01/hints/hint3-4.md deleted file mode 100644 index 766d3a9..0000000 --- a/Project#01/hints/hint3-4.md +++ /dev/null @@ -1,22 +0,0 @@ -If you print the angle between every possible combination of three atoms, you'll get lots of zeroes and angles between atoms that are far apart. To print mainly interesting angles, use if-else blocks to enforce these restrictions: -```c++ -if(i!=j && i!=k && j!=k) { } /* Skip coincidences */ -``` - -and -```c++ -if(i < j && j < k && R[i][j] < 4.0 && R[j][k] < 4.0) { } /* Skip atoms far apart (specifically with bond distances > 4.0 bohr) */ -``` - -Alternatively, you can limit the loop structure and just filter out the bond distances: -```c++ -for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - if(R[i][j] < 4.0 && R[j][k] < 4.0) { - ... - } - } - } -} -``` diff --git a/Project#01/hints/hint3-5.md b/Project#01/hints/hint3-5.md deleted file mode 100644 index c7f19d9..0000000 --- a/Project#01/hints/hint3-5.md +++ /dev/null @@ -1 +0,0 @@ -To compute the final bond angle, you must use the `acos()` function (arccos), which, like the `sqrt()` function, is part of the [C math library](http://en.wikipedia.org/wiki/Math.h). diff --git a/Project#01/hints/hint4-1.md b/Project#01/hints/hint4-1.md deleted file mode 100644 index e1f85cd..0000000 --- a/Project#01/hints/hint4-1.md +++ /dev/null @@ -1 +0,0 @@ -Note that, unlike the interatomic distance matrix and the three-dimensional bond angle array, the out-of-plane angles are not needed later in the program. Hence, there is no need to allocate any memory to store these angles. Simply print them one at a time. diff --git a/Project#01/hints/hint4-2.md b/Project#01/hints/hint4-2.md deleted file mode 100644 index 0cd31f4..0000000 --- a/Project#01/hints/hint4-2.md +++ /dev/null @@ -1,10 +0,0 @@ -A cross product between two vectors is another vector. Therefore, to store the cross product needed to compute a given out-of-plane angle, you need to store the x, y, and z components of the resulting vector, which you then use to compute a dot product with yet another vector. It is convenient to assign separate variables for each part of this calculation: -```c++ -ejkl_x = (ey[k][j] * ez[k][l] - ez[k][j] * ey[k][l]); -ejkl_y = (ez[k][j] * ex[k][l] - ex[k][j] * ez[k][l]); -ejkl_z = (ex[k][j] * ey[k][l] - ey[k][j] * ex[k][l]); - -exx = ejkl_x * ex[k][i]; -eyy = ejkl_y * ey[k][i]; -ezz = ejkl_z * ez[k][i]; -``` diff --git a/Project#01/hints/hint4-3.md b/Project#01/hints/hint4-3.md deleted file mode 100644 index ab6b32b..0000000 --- a/Project#01/hints/hint4-3.md +++ /dev/null @@ -1,8 +0,0 @@ -The final out-of-plane angle is computed using the `asin()` function. Note that since sine yields values between -1 and +1, the `asin()` function can only take arguments between -1.0 and +1.0. However, numerical precision in the calculation of the cross- and dot-products earlier in the calculation can yield results slightly outside this domain. Hence, you should test the argument of `asin()` before you call it: -```c++ - theta = (exx + eyy + ezz)/sin(phi[j][k][l]); - - if(theta < -1.0) theta = asin(-1.0); - else if(theta > 1.0) theta = asin(1.0); - else theta = asin(theta); -``` diff --git a/Project#01/hints/hint4-4.md b/Project#01/hints/hint4-4.md deleted file mode 100644 index 6aebb96..0000000 --- a/Project#01/hints/hint4-4.md +++ /dev/null @@ -1,8 +0,0 @@ -Just as for the bond angle code, we need to exclude ijkl combinations involving coincidences among the indices as well as distant atom pairs: -```c++ - if(i!=j && i!=k && i!=l && j!=k && j!=l && k!=l) { } /* Skip coincidences */ -``` -and -```c++ - if(R[i][k] < 4.0 && R[k][j] < 4.0 && R[k][l] < 4.0) { } /* Skip distant atom pairs */ -``` diff --git a/Project#01/hints/hint5-1.md b/Project#01/hints/hint5-1.md deleted file mode 100644 index 32e48c3..0000000 --- a/Project#01/hints/hint5-1.md +++ /dev/null @@ -1 +0,0 @@ -Just as for the out-of-plane angles, there is no need to store the torsional angles after they are printed, so no special memory allocation procedure is needed for this step. diff --git a/Project#01/hints/hint5-2.md b/Project#01/hints/hint5-2.md deleted file mode 100644 index 4a4ffb9..0000000 --- a/Project#01/hints/hint5-2.md +++ /dev/null @@ -1 +0,0 @@ -Just as for `asin()` in the out-of-plane angle calculation, you should check the argument to `acos()` to make sure it lies between -1.0 and +1.0. diff --git a/Project#01/hints/hint5-3.md b/Project#01/hints/hint5-3.md deleted file mode 100644 index 0613c4a..0000000 --- a/Project#01/hints/hint5-3.md +++ /dev/null @@ -1 +0,0 @@ -To print only the unique dihedral angles, it is straightforward in this case to limit the loop structure over i, j, k, and l to keep j < i, k < j, and l < k. Also, one should limit the printing only to atom pairs that are close together. diff --git a/Project#01/hints/hint5-4.md b/Project#01/hints/hint5-4.md deleted file mode 100644 index 43f3dd5..0000000 --- a/Project#01/hints/hint5-4.md +++ /dev/null @@ -1 +0,0 @@ -The sign of a torsional/dihedral angle among atoms **_i-j-k-l_** is positive (negative) if the vector along **_k-l_** lies to the right (left) of the plane formed by **_i-j-k_** when the plane is viewed along the **_j-k_** vector. diff --git a/Project#01/hints/hint6-1.md b/Project#01/hints/hint6-1.md deleted file mode 100644 index 27f9698..0000000 --- a/Project#01/hints/hint6-1.md +++ /dev/null @@ -1 +0,0 @@ -An excellent source for atomic masses and other physical constants is the [National Institute of Standard and Technology (NIST) website](http://physics.nist.gov/cgi-bin/Compositions/stand_alone.pl?ele=&ascii=html&isotype=some). diff --git a/Project#01/hints/hint6-2.md b/Project#01/hints/hint6-2.md deleted file mode 100644 index aea0a42..0000000 --- a/Project#01/hints/hint6-2.md +++ /dev/null @@ -1,10 +0,0 @@ -An elegant way to translate between the atomic number (z-value) of a given atom and its mass is to prepare a static array of the masses of the most abundant isotope of each element. I suggest preparing a header file containing a [global array](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Variable-Scope-and-Reference-Types#global-variables), e.g.: -```c++ - double masses[] = { - 0.0000000, - 1.007825, - 4.002603, - 6.015123, - ...}; -``` -Note that, for example, `masses[1] = 1.007825`, which is the correct atomic mass for a hydrogen atom. diff --git a/Project#01/hints/hint7-1.md b/Project#01/hints/hint7-1.md deleted file mode 100644 index 4aa7771..0000000 --- a/Project#01/hints/hint7-1.md +++ /dev/null @@ -1,45 +0,0 @@ -Here are two approaches for the [diagonalization](http://en.wikipedia.org/wiki/Diagonalizable_matrix) of the moment of inertia tensor: - -## Secular Determinant -Since the moment of inertia tensor is only a 3x3 matrix, a brute-force approach via the secular determinant is feasible: - - - -This leads to a cubic equation in λ, which one can solve directly. Have fun with that. - -## More General Algorithms -"Canned" algorithms are definitely the way to go for general matrix diagonalization. Most such algorithms are based on a two-step procedure: - - Reduction of the matrix to a tridiagonal form using the [Householder](http://en.wikipedia.org/wiki/Householder's_method) or Givens approaches. - - Diagonalization of the tridiagonal structure, either by solving its secular determinant or by other methods, e.g. [QR or QL decompositions](http://en.wikipedia.org/wiki/QR_decomposition). - -A convenient canned library for a wide range of linear algebraic operations is the [Eigen package](http://eigen.tuxfamily.org). This is a template-only library that provides a very clean interface for manipulating a large number of matrix types. You can either download and install the library from the [official website](http://eigen.tuxfamily.org) or just grab the [gzipped tarfile from here](../eigen.tar.gz). Unpack the library in the same directory as your source code, and you're ready to get started. - -To use the library to diagonalize your moment inertia tensor, follow these steps: - -- Add the following lines to your main source file below the inclusion of other headers: -```c++ -#include "Eigen/Dense" -#include "Eigen/Eigenvalues" -#include "Eigen/Core" - -typedef Eigen::Matrix Matrix; -``` -This code defines a new type called a `Matrix` that may be dynamically allocated and contains only doubles. -- Allocate your moment of inertia tensor by a line of code like: -```c++ -Matrix I(3,3); -``` -- Access or assign individual elements of the Matrix using parenthetical notation rather than brackets, e.g.: -```c++ -I(0,0) = 2.0; -``` -- The Eigen package makes it easy to examine your matrix using cout: -```c++ -cout << I << endl; -``` -- After you have built the moment of inertia tensor, you may compute its eigenvalues and eigenvectors as follows: -```c++ - Eigen::SelfAdjointEigenSolver solver(I); - Matrix evecs = solver.eigenvectors(); - Matrix evals = solver.eigenvalues(); -``` diff --git a/Project#01/hints/hint7-2.md b/Project#01/hints/hint7-2.md deleted file mode 100644 index 5a9a10c..0000000 --- a/Project#01/hints/hint7-2.md +++ /dev/null @@ -1 +0,0 @@ -Lots of useful and precise physical constants are available at the [National Institute of Standards and Technology website](http://physics.nist.gov/cuu/Constants/index.html?/codata86.html). diff --git a/Project#01/hints/step1-solution.md b/Project#01/hints/step1-solution.md deleted file mode 100644 index 9a1ffe4..0000000 --- a/Project#01/hints/step1-solution.md +++ /dev/null @@ -1,60 +0,0 @@ -```c++ -#include -#include -#include -#include - -using namespace std; - -int main() -{ - ifstream input("geom.dat"); - - int natom; - input >> natom; - - int *zval = new int[natom]; - double *x = new double[natom]; - double *y = new double[natom]; - double *z = new double[natom]; - - for(int i=0; i < natom; i++) - input >> zval[i] >> x[i] >> y[i] >> z[i]; - - input.close(); - - cout << "Number of atoms: " << natom << endl; - cout << "Input Cartesian coordinates:\n"; - for(int i=0; i < natom; i++) - printf("%d %20.12f %20.12f %20.12f\n", (int) zval[i], x[i], y[i], z[i]); - - delete[] zval; - delete[] x; delete[] y; delete[] z; - - return 0; -} -``` - -An even more elegant solution would be to couple the above to the [Molecule class](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Classes-and-Objects) we defined earlier in the Fundamentals section: -```c++ -#include "molecule.h" -#include -#include -#include -#include - -using namespace std; - -int main() -{ - Molecule mol("geom.dat", 0); - - cout << "Number of atoms: " << mol.natom << endl; - cout << "Input Cartesian coordinates:\n"; - mol.print_geom(); - - return 0; -} -``` - - diff --git a/Project#01/hints/step2-solution.md b/Project#01/hints/step2-solution.md deleted file mode 100644 index bc24c9e..0000000 --- a/Project#01/hints/step2-solution.md +++ /dev/null @@ -1,63 +0,0 @@ -Here we use the Molecule class we've been working on so far, and thanks to the new "bond()" function, we don't need to worry about storing the distances in a matrix: - -```c++ -#include "molecule.h" -#include -#include -#include -#include -#include - -using namespace std; - -int main() -{ - Molecule mol("geom.dat", 0); - - cout << "Number of atoms: " << mol.natom << endl; - cout << "Input Cartesian coordinates:\n"; - mol.print_geom(); - - cout << "Interatomic distances (bohr):\n"; - for(int i=0; i < mol.natom; i++) - for(int j=0; j < i; j++) - printf("%d %d %8.5f\n", i, j, mol.bond(i,j)); - - return 0; -} -``` - -The output from the above program for the acetaldehyde test case is: -``` -Number of atoms: 7 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 -Interatomic distances (bohr): -1 0 2.84511 -2 0 4.55395 -2 1 2.29803 -3 0 4.19912 -3 1 2.09811 -3 2 3.81330 -4 0 2.06517 -4 1 4.04342 -4 2 4.84040 -4 3 5.87463 -5 0 2.07407 -5 1 4.05133 -5 2 5.89151 -5 3 4.83836 -5 4 3.38971 -6 0 2.07407 -6 1 4.05133 -6 2 5.89151 -6 3 4.83836 -6 4 3.38971 -6 5 3.33994 -``` diff --git a/Project#01/hints/step3-solution.md b/Project#01/hints/step3-solution.md deleted file mode 100644 index 8de6c2d..0000000 --- a/Project#01/hints/step3-solution.md +++ /dev/null @@ -1,128 +0,0 @@ -Here again we've extended the Molecule class to compute the bond angles without storing them. This also required the addition of a new function to compute the Cartesian unit vectors on the fly, whose declaration we add to the member functions of molecule.h: -```c++ -#include - -using namespace std; - -class Molecule -{ - public: - int natom; - int charge; - int *zvals; - double **geom; - string point_group; - - void print_geom(); - void rotate(double phi); - void translate(double x, double y, double z); - double bond(int atom1, int atom2); - double angle(int atom1, int atom2, int atom3); - double torsion(int atom1, int atom2, int atom3, int atom4); - double unit(int cart, int atom1, int atom2); - - Molecule(const char *filename, int q); - ~Molecule(); -}; -``` - -Now the two new functions added to molecule.cc: -```c++ -// Returns the value of the unit vector between atoms a and b -// in the cart direction (cart=0=x, cart=1=y, cart=2=z) -double Molecule::unit(int cart, int a, int b) -{ - return -(geom[a][cart]-geom[b][cart])/bond(a,b); -} - -// Returns the angle between atoms a, b, and c in radians -double Molecule::angle(int a, int b, int c) -{ - return acos(unit(0,b,a) * unit(0,b,c) + unit(1,b,a) * unit(1,b,c) + unit(2,b,a) * unit(2,b,c)); -} -``` - -And finally, the code that makes use of the above: - -```c++ -#include "molecule.h" -#include -#include -#include -#include -#include - -using namespace std; - -int main() -{ - Molecule mol("geom.dat", 0); - - cout << "Number of atoms: " << mol.natom << endl; - cout << "Input Cartesian coordinates:\n"; - mol.print_geom(); - - cout << "Interatomic distances (bohr):\n"; - for(int i=0; i < mol.natom; i++) - for(int j=0; j < i; j++) - printf("%d %d %8.5f\n", i, j, mol.bond(i,j)); - - cout << "\nBond angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0) - printf("%2d-%2d-%2d %10.6f\n", i, j, k, mol.angle(i,j,k)*(180.0/acos(-1.0))); - } - } - } - - return 0; -} -``` -Note that the value of π is obtained with machine precision using `acos(-1.0)`. - -The above code produces the following output for the acetaldehyde test case: - -``` -Number of atoms: 7 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 -Interatomic distances (bohr): -1 0 2.84511 -2 0 4.55395 -2 1 2.29803 -3 0 4.19912 -3 1 2.09811 -3 2 3.81330 -4 0 2.06517 -4 1 4.04342 -4 2 4.84040 -4 3 5.87463 -5 0 2.07407 -5 1 4.05133 -5 2 5.89151 -5 3 4.83836 -5 4 3.38971 -6 0 2.07407 -6 1 4.05133 -6 2 5.89151 -6 3 4.83836 -6 4 3.38971 -6 5 3.33994 - -Bond angles: - 2- 1- 0 124.268308 - 3- 1- 0 115.479341 - 3- 2- 1 28.377448 - 5- 4- 0 35.109529 - 6- 4- 0 35.109529 - 6- 5- 0 36.373677 - 6- 5- 4 60.484476 -``` diff --git a/Project#01/hints/step4-solution.md b/Project#01/hints/step4-solution.md deleted file mode 100644 index 5c3ae48..0000000 --- a/Project#01/hints/step4-solution.md +++ /dev/null @@ -1,174 +0,0 @@ -We've added a new function to the Molecule class for computing the out-of-plane angles. Here's the new molecule.h: - -```c++ -#include - -using namespace std; - -class Molecule -{ - public: - int natom; - int charge; - int *zvals; - double **geom; - string point_group; - - void print_geom(); - void rotate(double phi); - void translate(double x, double y, double z); - double bond(int atom1, int atom2); - double angle(int atom1, int atom2, int atom3); - double torsion(int atom1, int atom2, int atom3, int atom4); - double oop(int atom1, int atom2, int atom3, int atom4); - double unit(int cart, int atom1, int atom2); - - Molecule(const char *filename, int q); - ~Molecule(); -}; -``` - -Here's the new `oop()` function for molecule.cc: - -```c++ -double Molecule::oop(int a, int b, int c, int d) -{ - double ebcd_x = (unit(1,c,b) * unit(2,c,d) - unit(2,c,b) * unit(1,c,d)); - double ebcd_y = (unit(2,c,b) * unit(0,c,d) - unit(0,c,b) * unit(2,c,d)); - double ebcd_z = (unit(0,c,b) * unit(1,c,d) - unit(1,c,b) * unit(0,c,d)); - - double exx = ebcd_x * unit(0,c,a); - double eyy = ebcd_y * unit(1,c,a); - double ezz = ebcd_z * unit(2,c,a); - - double theta = (exx + eyy + ezz)/sin(angle(b,c,d)); - - if(theta < -1.0) theta = asin(-1.0); - else if(theta > 1.0) theta = asin(1.0); - else theta = asin(theta); - - return theta; -} -``` - -And finally the new code that makes use of the class: - -```c++ -#include "molecule.h" -#include -#include -#include -#include -#include - -using namespace std; - -int main() -{ - Molecule mol("geom.dat", 0); - - cout << "Number of atoms: " << mol.natom << endl; - cout << "Input Cartesian coordinates:\n"; - mol.print_geom(); - - cout << "Interatomic distances (bohr):\n"; - for(int i=0; i < mol.natom; i++) - for(int j=0; j < i; j++) - printf("%d %d %8.5f\n", i, j, mol.bond(i,j)); - - cout << "\nBond angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0) - printf("%2d-%2d-%2d %10.6f\n", i, j, k, mol.angle(i,j,k)*(180.0/acos(-1.0))); - } - } - } - - cout << "\nOut-of-Plane angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int k=0; k < mol.natom; k++) { - for(int j=0; j < mol.natom; j++) { - for(int l=0; l < j; l++) { - if(i!=j && i!=k && i!=l && j!=k && k!=l && mol.bond(i,k) < 4.0 && mol.bond(k,j) < 4.0 && mol.bond(k,l) < 4.0) - printf("%2d-%2d-%2d-%2d %10.6f\n", i, j, k, l, mol.oop(i,j,k,l)*(180.0/acos(-1.0))); - } - } - } - } - - return 0; -} -``` - -The above code produces the following output for the acetaldehyde test case: - -``` -Number of atoms: 7 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 -Interatomic distances (bohr): -1 0 2.84511 -2 0 4.55395 -2 1 2.29803 -3 0 4.19912 -3 1 2.09811 -3 2 3.81330 -4 0 2.06517 -4 1 4.04342 -4 2 4.84040 -4 3 5.87463 -5 0 2.07407 -5 1 4.05133 -5 2 5.89151 -5 3 4.83836 -5 4 3.38971 -6 0 2.07407 -6 1 4.05133 -6 2 5.89151 -6 3 4.83836 -6 4 3.38971 -6 5 3.33994 - -Bond angles: - 2- 1- 0 124.268308 - 3- 1- 0 115.479341 - 3- 2- 1 28.377448 - 5- 4- 0 35.109529 - 6- 4- 0 35.109529 - 6- 5- 0 36.373677 - 6- 5- 4 60.484476 - -Out-of-plane angles: - 0- 3- 1- 2 -0.000000 - 0- 6- 4- 5 19.939726 - 0- 6- 5- 4 -19.850523 - 0- 5- 6- 4 19.850523 - 1- 5- 0- 4 53.678778 - 1- 6- 0- 4 -53.678778 - 1- 6- 0- 5 54.977064 - 2- 3- 1- 0 0.000000 - 3- 2- 1- 0 -0.000000 - 4- 5- 0- 1 -53.651534 - 4- 6- 0- 1 53.651534 - 4- 6- 0- 5 -54.869992 - 4- 6- 5- 0 29.885677 - 4- 5- 6- 0 -29.885677 - 5- 4- 0- 1 53.626323 - 5- 6- 0- 1 -56.277112 - 5- 6- 0- 4 56.194621 - 5- 6- 4- 0 -30.558964 - 5- 4- 6- 0 31.064344 - 6- 4- 0- 1 -53.626323 - 6- 5- 0- 1 56.277112 - 6- 5- 0- 4 -56.194621 - 6- 5- 4- 0 30.558964 - 6- 4- 5- 0 -31.064344 -``` diff --git a/Project#01/hints/step5-solution.md b/Project#01/hints/step5-solution.md deleted file mode 100644 index 7c437d3..0000000 --- a/Project#01/hints/step5-solution.md +++ /dev/null @@ -1,177 +0,0 @@ -Now we've added a new member function to the Molecule class: -```c++ -// Computes the angle between planes a-b-c and b-c-d -double Molecule::torsion(int a, int b, int c, int d) -{ - double eabc_x = (unit(1,b,a)*unit(2,b,c) - unit(2,b,a)*unit(1,b,c)); - double eabc_y = (unit(2,b,a)*unit(0,b,c) - unit(0,b,a)*unit(2,b,c)); - double eabc_z = (unit(0,b,a)*unit(1,b,c) - unit(1,b,a)*unit(0,b,c)); - - double ebcd_x = (unit(1,c,b)*unit(2,c,d) - unit(2,c,b)*unit(1,c,d)); - double ebcd_y = (unit(2,c,b)*unit(0,c,d) - unit(0,c,b)*unit(2,c,d)); - double ebcd_z = (unit(0,c,b)*unit(1,c,d) - unit(1,c,b)*unit(0,c,d)); - - double exx = eabc_x * ebcd_x; - double eyy = eabc_y * ebcd_y; - double ezz = eabc_z * ebcd_z; - - double tau = (exx + eyy + ezz)/(sin(angle(a,b,c)) * sin(angle(b,c,d))); - - if(tau < -1.0) tau = acos(-1.0); - else if(tau > 1.0) tau = acos(1.0); - else tau = acos(tau); - - // Compute the sign of the torsion - double cross_x = eabc_y * ebcd_z - eabc_z * ebcd_y; - double cross_y = eabc_z * ebcd_x - eabc_x * ebcd_z; - double cross_z = eabc_x * ebcd_y - eabc_y * ebcd_x; - double norm = cross_x*cross_x + cross_y*cross_y + cross_z*cross_z; - cross_x /= norm; - cross_y /= norm; - cross_z /= norm; - double sign = 1.0; - double dot = cross_x*unit(0,b,c)+cross_y*unit(1,b,c)+cross_z*unit(2,b,c); - if(dot < 0.0) sign = -1.0; - - return tau*sign; -} -``` - -And we use the new function in the code as follows: - -```c++ -#include -#include -#include -#include -#include -#include "molecule.h" - -using namespace std; - -int main() -{ - Molecule mol("geom.dat", 0); - - cout << "Number of atoms: " << mol.natom << endl; - cout << "Input Cartesian coordinates:\n"; - mol.print_geom(); - - cout << "Interatomic distances (bohr):\n"; - for(int i=0; i < mol.natom; i++) - for(int j=0; j < i; j++) - printf("%d %d %8.5f\n", i, j, mol.bond(i,j)); - - cout << "\nBond angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0) - printf("%2d-%2d-%2d %10.6f\n", i, j, k, mol.angle(i,j,k)*(180.0/acos(-1.0))); - } - } - } - - cout << "\nOut-of-Plane angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int k=0; k < mol.natom; k++) { - for(int j=0; j < mol.natom; j++) { - for(int l=0; l < j; l++) { - if(i!=j && i!=k && i!=l && j!=k && k!=l && mol.bond(i,k) < 4.0 && mol.bond(k,j) < 4.0 && mol.bond(k,l) < 4.0) - printf("%2d-%2d-%2d-%2d %10.6f\n", i, j, k, l, mol.oop(i,j,k,l)*(180.0/acos(-1.0))); - } - } - } - } - - cout << "\nTorsional angles:\n\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - for(int l=0; l < k; l++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0 && mol.bond(k,l) < 4.0) - printf("%2d-%2d-%2d-%2d %10.6f\n", i, j, k, l, mol.torsion(i,j,k,l)*(180.0/acos(-1.0))); - } - } - } - } - - return 0; -} -``` - -The above code produces the following output when applied to the acetaldehyde test case: - -``` -Number of atoms: 7 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 -Interatomic distances (bohr): -1 0 2.84511 -2 0 4.55395 -2 1 2.29803 -3 0 4.19912 -3 1 2.09811 -3 2 3.81330 -4 0 2.06517 -4 1 4.04342 -4 2 4.84040 -4 3 5.87463 -5 0 2.07407 -5 1 4.05133 -5 2 5.89151 -5 3 4.83836 -5 4 3.38971 -6 0 2.07407 -6 1 4.05133 -6 2 5.89151 -6 3 4.83836 -6 4 3.38971 -6 5 3.33994 - -Bond angles: - 0- 1- 2 124.268308 - 0- 1- 3 115.479341 - 0- 4- 5 35.109529 - 0- 4- 6 35.109529 - 0- 5- 6 36.373677 - 1- 2- 3 28.377448 - 4- 5- 6 60.484476 - -Out-of-plane angles: - 0- 3- 1- 2 -0.000000 - 0- 6- 4- 5 19.939726 - 0- 6- 5- 4 -19.850523 - 0- 5- 6- 4 19.850523 - 1- 5- 0- 4 53.678778 - 1- 6- 0- 4 -53.678778 - 1- 6- 0- 5 54.977064 - 2- 3- 1- 0 0.000000 - 3- 2- 1- 0 -0.000000 - 4- 5- 0- 1 -53.651534 - 4- 6- 0- 1 53.651534 - 4- 6- 0- 5 -54.869992 - 4- 6- 5- 0 29.885677 - 4- 5- 6- 0 -29.885677 - 5- 4- 0- 1 53.626323 - 5- 6- 0- 1 -56.277112 - 5- 6- 0- 4 56.194621 - 5- 6- 4- 0 -30.558964 - 5- 4- 6- 0 31.064344 - 6- 4- 0- 1 -53.626323 - 6- 5- 0- 1 56.277112 - 6- 5- 0- 4 -56.194621 - 6- 5- 4- 0 30.558964 - 6- 4- 5- 0 -31.064344 - -Torsional angles: - - 3- 2- 1- 0 180.000000 - 6- 5- 4- 0 36.366799 -``` diff --git a/Project#01/hints/step6-solution.md b/Project#01/hints/step6-solution.md deleted file mode 100644 index 4ea9d7e..0000000 --- a/Project#01/hints/step6-solution.md +++ /dev/null @@ -1,163 +0,0 @@ -Note that the header file, `masses.h` is not provided. See the [Hint](./hint6-2.md) to learn how to construct it. Also note that we've made convenient use of our `translate()` member function for the Molecule class. - -```c++ -#include "molecule.h" -#include "masses.h" - -#include -#include -#include -#include -#include - -using namespace std; - -int main() -{ - Molecule mol("geom.dat", 0); - - cout << "Number of atoms: " << mol.natom << endl; - cout << "Input Cartesian coordinates:\n"; - mol.print_geom(); - - cout << "Interatomic distances (bohr):\n"; - for(int i=0; i < mol.natom; i++) - for(int j=0; j < i; j++) - printf("%d %d %8.5f\n", i, j, mol.bond(i,j)); - - cout << "\nBond angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0) - printf("%2d-%2d-%2d %10.6f\n", i, j, k, mol.angle(i,j,k)*(180.0/acos(-1.0))); - } - } - } - - cout << "\nOut-of-Plane angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int k=0; k < mol.natom; k++) { - for(int j=0; j < mol.natom; j++) { - for(int l=0; l < j; l++) { - if(i!=j && i!=k && i!=l && j!=k && k!=l && mol.bond(i,k) < 4.0 && mol.bond(k,j) < 4.0 && mol.bond(k,l) < 4.0) - printf("%2d-%2d-%2d-%2d %10.6f\n", i, j, k, l, mol.oop(i,j,k,l)*(180.0/acos(-1.0))); - } - } - } - } - - cout << "\nTorsional angles:\n\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - for(int l=0; l < k; l++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0 && mol.bond(k,l) < 4.0) - printf("%2d-%2d-%2d-%2d %10.6f\n", i, j, k, l, mol.torsion(i,j,k,l)*(180.0/acos(-1.0))); - } - } - } - } - - /* find the center of mass (COM) */ - double M = 0.0; - for(int i=0; i < mol.atom; i++) M += an2masses[(int) mol.zvals[i]]; - - double xcm=0.0; - double ycm=0.0; - double zcm=0.0; - double mi; - for(int i=0; i < mol.atom; i++) { - mi = an2masses[(int) mol.zvals[i]]; - xcm += mi * mol.geom[i][0]; - ycm += mi * mol.geom[i][1]; - zcm += mi * mol.geom[i][2]; - } - xcm /= M; - ycm /= M; - zcm /= M; - printf("\nMolecular center of mass: %12.8f %12.8f %12.8f\n", xcm, ycm, zcm); - - mol.translate(-xcm, -ycm, -zcm); - - return 0; -} -``` - -The above code produces the following output when applied to the acetaldehyde test case: - -``` -Number of atoms: 7 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 -Interatomic distances (bohr): -1 0 2.84511 -2 0 4.55395 -2 1 2.29803 -3 0 4.19912 -3 1 2.09811 -3 2 3.81330 -4 0 2.06517 -4 1 4.04342 -4 2 4.84040 -4 3 5.87463 -5 0 2.07407 -5 1 4.05133 -5 2 5.89151 -5 3 4.83836 -5 4 3.38971 -6 0 2.07407 -6 1 4.05133 -6 2 5.89151 -6 3 4.83836 -6 4 3.38971 -6 5 3.33994 - -Bond angles: - 0- 1- 2 124.268308 - 0- 1- 3 115.479341 - 0- 4- 5 35.109529 - 0- 4- 6 35.109529 - 0- 5- 6 36.373677 - 1- 2- 3 28.377448 - 4- 5- 6 60.484476 - -Out-of-plane angles: - 0- 3- 1- 2 -0.000000 - 0- 6- 4- 5 19.939726 - 0- 6- 5- 4 -19.850523 - 0- 5- 6- 4 19.850523 - 1- 5- 0- 4 53.678778 - 1- 6- 0- 4 -53.678778 - 1- 6- 0- 5 54.977064 - 2- 3- 1- 0 0.000000 - 3- 2- 1- 0 -0.000000 - 4- 5- 0- 1 -53.651534 - 4- 6- 0- 1 53.651534 - 4- 6- 0- 5 -54.869992 - 4- 6- 5- 0 29.885677 - 4- 5- 6- 0 -29.885677 - 5- 4- 0- 1 53.626323 - 5- 6- 0- 1 -56.277112 - 5- 6- 0- 4 56.194621 - 5- 6- 4- 0 -30.558964 - 5- 4- 6- 0 31.064344 - 6- 4- 0- 1 -53.626323 - 6- 5- 0- 1 56.277112 - 6- 5- 0- 4 -56.194621 - 6- 5- 4- 0 30.558964 - 6- 4- 5- 0 -31.064344 - -Torsional angles: - - 3- 2- 1- 0 180.000000 - 6- 5- 4- 0 36.366799 - -Molecular center of mass: 0.64494926 0.00000000 2.31663792 -``` diff --git a/Project#01/hints/step7-solution.md b/Project#01/hints/step7-solution.md deleted file mode 100644 index babca70..0000000 --- a/Project#01/hints/step7-solution.md +++ /dev/null @@ -1,232 +0,0 @@ -Note that this is only the code for the `main()` function. The Eigen package, which provides the Matrix class and associated diagonalization capabilities is described in a [hint](./hint7-1.md). - -```c++ -#include "molecule.h" -#include "masses.h" - -#include -#include -#include -#include -#include - -#include "Eigen/Dense" -#include "Eigen/Eigenvalues" -#include "Eigen/Core" - -typedef Eigen::Matrix Matrix; -typedef Eigen::Matrix Vector; - -using namespace std; - -int main() -{ - Molecule mol("geom.dat", 0); - - cout << "Number of atoms: " << mol.natom << endl; - cout << "Input Cartesian coordinates:\n"; - mol.print_geom(); - - cout << "Interatomic distances (bohr):\n"; - for(int i=0; i < mol.natom; i++) - for(int j=0; j < i; j++) - printf("%d %d %8.5f\n", i, j, mol.bond(i,j)); - - cout << "\nBond angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0) - printf("%2d-%2d-%2d %10.6f\n", i, j, k, mol.angle(i,j,k)*(180.0/acos(-1.0))); - } - } - } - - cout << "\nOut-of-Plane angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int k=0; k < mol.natom; k++) { - for(int j=0; j < mol.natom; j++) { - for(int l=0; l < j; l++) { - if(i!=j && i!=k && i!=l && j!=k && k!=l && mol.bond(i,k) < 4.0 && mol.bond(k,j) < 4.0 && mol.bond(k,l) < 4.0) - printf("%2d-%2d-%2d-%2d %10.6f\n", i, j, k, l, mol.oop(i,j,k,l)*(180.0/acos(-1.0))); - } - } - } - } - - cout << "\nTorsional angles:\n\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - for(int l=0; l < k; l++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0 && mol.bond(k,l) < 4.0) - printf("%2d-%2d-%2d-%2d %10.6f\n", i, j, k, l, mol.torsion(i,j,k,l)*(180.0/acos(-1.0))); - } - } - } - } - - /* find the center of mass (COM) */ - double M = 0.0; - for(int i=0; i < natom; i++) M += an2masses[(int) mol.zvals[i]]; - - double xcm=0.0; - double ycm=0.0; - double zcm=0.0; - double mi; - for(int i=0; i < natom; i++) { - mi = an2masses[(int) mol.zvals[i]]; - xcm += mi * mol.geom[i][0]; - ycm += mi * mol.geom[i][1]; - zcm += mi * mol.geom[i][2]; - } - xcm /= M; - ycm /= M; - zcm /= M; - printf("\nMolecular center of mass: %12.8f %12.8f %12.8f\n", xcm, ycm, zcm); - - mol.translate(-xcm, -ycm, -zcm); - - Matrix I(3,3); - - for(int i=0; i < mol.natom; i++) { - mi = masses[(int) mol.zvals[i]]; - I(0,0) += mi * (mol.geom[i][1]*mol.geom[i][1] + mol.geom[i][2]*mol.geom[i][2]); - I(1,1) += mi * (mol.geom[i][0]*mol.geom[i][0] + mol.geom[i][2]*mol.geom[i][2]); - I(2,2) += mi * (mol.geom[i][0]*mol.geom[i][0] + mol.geom[i][1]*mol.geom[i][1]); - I(0,1) -= mi * mol.geom[i][0]*mol.geom[i][1]; - I(0,2) -= mi * mol.geom[i][0]*mol.geom[i][2]; - I(1,2) -= mi * mol.geom[i][1]*mol.geom[i][2]; - } - - I(1,0) = I(0,1); - I(2,0) = I(0,2); - I(2,1) = I(1,2); - - cout << "\nMoment of inertia tensor (amu bohr^2):\n"; - cout << I << endl; - - // find the principal moments - Eigen::SelfAdjointEigenSolver solver(I); - Matrix evecs = solver.eigenvectors(); - Matrix evals = solver.eigenvalues(); - - cout << "\nPrincipal moments of inertia (amu * bohr^2):\n"; - cout << evals << endl; - - double conv = 0.529177249 * 0.529177249; - cout << "\nPrincipal moments of inertia (amu * AA^2):\n"; - cout << evals * conv << endl; - - conv = 1.6605402E-24 * 0.529177249E-8 * 0.529177249E-8; - cout << "\nPrincipal moments of inertia (g * cm^2):\n"; - cout << evals * conv << endl; - - // classify the rotor - if(mol.natom == 2) cout << "\nMolecule is diatomic.\n"; - else if(evals(0) < 1e-4) cout << "\nMolecule is linear.\n"; - else if((fabs(evals(0) - evals(1)) < 1e-4) && (fabs(evals(1) - evals(2)) < 1e-4)) - cout << "\nMolecule is a spherical top.\n"; - else if((fabs(evals(0) - evals(1)) < 1e-4) && (fabs(evals(1) - evals(2)) > 1e-4)) - cout << "\nMolecule is an oblate symmetric top.\n"; - else if((fabs(evals(0) - evals(1)) > 1e-4) && (fabs(evals(1) - evals(2)) < 1e-4)) - cout << "\nMolecule is a prolate symmetric top.\n"; - else cout << "\nMolecule is an asymmetric top.\n"; - - return 0; -} -``` - -The above code produces the following output for the acetaldehyde test case: - -``` -Number of atoms: 7 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 -Interatomic distances (bohr): -1 0 2.84511 -2 0 4.55395 -2 1 2.29803 -3 0 4.19912 -3 1 2.09811 -3 2 3.81330 -4 0 2.06517 -4 1 4.04342 -4 2 4.84040 -4 3 5.87463 -5 0 2.07407 -5 1 4.05133 -5 2 5.89151 -5 3 4.83836 -5 4 3.38971 -6 0 2.07407 -6 1 4.05133 -6 2 5.89151 -6 3 4.83836 -6 4 3.38971 -6 5 3.33994 - -Bond angles: - 0- 1- 2 124.268308 - 0- 1- 3 115.479341 - 0- 4- 5 35.109529 - 0- 4- 6 35.109529 - 0- 5- 6 36.373677 - 1- 2- 3 28.377448 - 4- 5- 6 60.484476 - -Out-of-plane angles: - 0- 3- 1- 2 -0.000000 - 0- 6- 4- 5 19.939726 - 0- 6- 5- 4 -19.850523 - 0- 5- 6- 4 19.850523 - 1- 5- 0- 4 53.678778 - 1- 6- 0- 4 -53.678778 - 1- 6- 0- 5 54.977064 - 2- 3- 1- 0 0.000000 - 3- 2- 1- 0 -0.000000 - 4- 5- 0- 1 -53.651534 - 4- 6- 0- 1 53.651534 - 4- 6- 0- 5 -54.869992 - 4- 6- 5- 0 29.885677 - 4- 5- 6- 0 -29.885677 - 5- 4- 0- 1 53.626323 - 5- 6- 0- 1 -56.277112 - 5- 6- 0- 4 56.194621 - 5- 6- 4- 0 -30.558964 - 5- 4- 6- 0 31.064344 - 6- 4- 0- 1 -53.626323 - 6- 5- 0- 1 56.277112 - 6- 5- 0- 4 -56.194621 - 6- 5- 4- 0 30.558964 - 6- 4- 5- 0 -31.064344 - -Torsional angles: - - 3- 2- 1- 0 180.000000 - 6- 5- 4- 0 36.366799 - -Molecular center of mass: 0.64494926 0.00000000 2.31663792 - -Moment of inertia tensor (amu bohr^2): - 156.154091561645 0.000000000000 -52.855584120568 - 0.000000000000 199.371126996236 0.000000000000 - -52.855584120568 0.000000000000 54.459548882464 - -Principal moments of inertia (amu * bohr^2): - 31.964078 178.649562 199.371127 - -Principal moments of inertia (amu * AA^2): - 8.950855 50.026980 55.829610 - -Principal moments of inertia (g * cm^2): - 1.486325e-39 8.307181e-39 9.270731e-39 - -Molecule is an asymmetric top. -``` diff --git a/Project#01/hints/step8-solution.md b/Project#01/hints/step8-solution.md deleted file mode 100644 index f85cabf..0000000 --- a/Project#01/hints/step8-solution.md +++ /dev/null @@ -1,252 +0,0 @@ -Note that this is only the code for the `main()` function. The Eigen package, which provides the Matrix class and associated diagonalization capabilities is described in a [hint](./hint7-1.md). - -```c++ -#include "molecule.h" -#include "masses.h" - -#include -#include -#include -#include -#include - -#include "Eigen/Dense" -#include "Eigen/Eigenvalues" -#include "Eigen/Core" - -typedef Eigen::Matrix Matrix; -typedef Eigen::Matrix Vector; - -using namespace std; - -int main() -{ - Molecule mol("geom.dat", 0); - - cout << "Number of atoms: " << mol.natom << endl; - cout << "Input Cartesian coordinates:\n"; - mol.print_geom(); - - cout << "Interatomic distances (bohr):\n"; - for(int i=0; i < mol.natom; i++) - for(int j=0; j < i; j++) - printf("%d %d %8.5f\n", i, j, mol.bond(i,j)); - - cout << "\nBond angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0) - printf("%2d-%2d-%2d %10.6f\n", i, j, k, mol.angle(i,j,k)*(180.0/acos(-1.0))); - } - } - } - - cout << "\nOut-of-Plane angles:\n"; - for(int i=0; i < mol.natom; i++) { - for(int k=0; k < mol.natom; k++) { - for(int j=0; j < mol.natom; j++) { - for(int l=0; l < j; l++) { - if(i!=j && i!=k && i!=l && j!=k && k!=l && mol.bond(i,k) < 4.0 && mol.bond(k,j) < 4.0 && mol.bond(k,l) < 4.0) - printf("%2d-%2d-%2d-%2d %10.6f\n", i, j, k, l, mol.oop(i,j,k,l)*(180.0/acos(-1.0))); - } - } - } - } - - cout << "\nTorsional angles:\n\n"; - for(int i=0; i < mol.natom; i++) { - for(int j=0; j < i; j++) { - for(int k=0; k < j; k++) { - for(int l=0; l < k; l++) { - if(mol.bond(i,j) < 4.0 && mol.bond(j,k) < 4.0 && mol.bond(k,l) < 4.0) - printf("%2d-%2d-%2d-%2d %10.6f\n", i, j, k, l, mol.torsion(i,j,k,l)*(180.0/acos(-1.0))); - } - } - } - } - - /* find the center of mass (COM) */ - double M = 0.0; - for(int i=0; i < natom; i++) M += an2masses[(int) mol.zvals[i]]; - - double xcm=0.0; - double ycm=0.0; - double zcm=0.0; - double mi; - for(int i=0; i < natom; i++) { - mi = an2masses[(int) mol.zvals[i]]; - xcm += mi * mol.geom[i][0]; - ycm += mi * mol.geom[i][1]; - zcm += mi * mol.geom[i][2]; - } - xcm /= M; - ycm /= M; - zcm /= M; - printf("\nMolecular center of mass: %12.8f %12.8f %12.8f\n", xcm, ycm, zcm); - - mol.translate(-xcm, -ycm, -zcm); - - Matrix I(3,3); - - for(int i=0; i < mol.natom; i++) { - mi = masses[(int) mol.zvals[i]]; - I(0,0) += mi * (mol.geom[i][1]*mol.geom[i][1] + mol.geom[i][2]*mol.geom[i][2]); - I(1,1) += mi * (mol.geom[i][0]*mol.geom[i][0] + mol.geom[i][2]*mol.geom[i][2]); - I(2,2) += mi * (mol.geom[i][0]*mol.geom[i][0] + mol.geom[i][1]*mol.geom[i][1]); - I(0,1) -= mi * mol.geom[i][0]*mol.geom[i][1]; - I(0,2) -= mi * mol.geom[i][0]*mol.geom[i][2]; - I(1,2) -= mi * mol.geom[i][1]*mol.geom[i][2]; - } - - I(1,0) = I(0,1); - I(2,0) = I(0,2); - I(2,1) = I(1,2); - - cout << "\nMoment of inertia tensor (amu bohr^2):\n"; - cout << I << endl; - - // find the principal moments - Eigen::SelfAdjointEigenSolver solver(I); - Matrix evecs = solver.eigenvectors(); - Matrix evals = solver.eigenvalues(); - - cout << "\nPrincipal moments of inertia (amu * bohr^2):\n"; - cout << evals << endl; - - double conv = 0.529177249 * 0.529177249; - cout << "\nPrincipal moments of inertia (amu * AA^2):\n"; - cout << evals * conv << endl; - - conv = 1.6605402E-24 * 0.529177249E-8 * 0.529177249E-8; - cout << "\nPrincipal moments of inertia (g * cm^2):\n"; - cout << evals * conv << endl; - - // classify the rotor - if(mol.natom == 2) cout << "\nMolecule is diatomic.\n"; - else if(evals(0) < 1e-4) cout << "\nMolecule is linear.\n"; - else if((fabs(evals(0) - evals(1)) < 1e-4) && (fabs(evals(1) - evals(2)) < 1e-4)) - cout << "\nMolecule is a spherical top.\n"; - else if((fabs(evals(0) - evals(1)) < 1e-4) && (fabs(evals(1) - evals(2)) > 1e-4)) - cout << "\nMolecule is an oblate symmetric top.\n"; - else if((fabs(evals(0) - evals(1)) > 1e-4) && (fabs(evals(1) - evals(2)) < 1e-4)) - cout << "\nMolecule is a prolate symmetric top.\n"; - else cout << "\nMolecule is an asymmetric top.\n"; - - // compute the rotational constants - double _pi = acos(-1.0); - conv = 6.6260755E-34/(8.0 * _pi * _pi); - conv /= 1.6605402E-27 * 0.529177249E-10 * 0.529177249E-10; - conv *= 1e-6; - cout << "\nRotational constants (MHz):\n"; - cout << "\tA = " << conv/evals(0) << "\t B = " << conv/evals(1) << "\t C = " << conv/evals(2) << endl; - - conv = 6.6260755E-34/(8.0 * _pi * _pi); - conv /= 1.6605402E-27 * 0.529177249E-10 * 0.529177249E-10; - conv /= 2.99792458E10; - cout << "\nRotational constants (cm-1):\n"; - cout << "\tA = " << conv/evals(0) << "\t B = " << conv/evals(1) << "\t C = " << conv/evals(2) << endl; - - return 0; -} -``` - -The above code produces the following output for the acetaldehyde test case: - -``` -Number of atoms: 7 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 -Interatomic distances (bohr): -1 0 2.84511 -2 0 4.55395 -2 1 2.29803 -3 0 4.19912 -3 1 2.09811 -3 2 3.81330 -4 0 2.06517 -4 1 4.04342 -4 2 4.84040 -4 3 5.87463 -5 0 2.07407 -5 1 4.05133 -5 2 5.89151 -5 3 4.83836 -5 4 3.38971 -6 0 2.07407 -6 1 4.05133 -6 2 5.89151 -6 3 4.83836 -6 4 3.38971 -6 5 3.33994 - -Bond angles: - 0- 1- 2 124.268308 - 0- 1- 3 115.479341 - 0- 4- 5 35.109529 - 0- 4- 6 35.109529 - 0- 5- 6 36.373677 - 1- 2- 3 28.377448 - 4- 5- 6 60.484476 - -Out-of-plane angles: - 0- 3- 1- 2 -0.000000 - 0- 6- 4- 5 19.939726 - 0- 6- 5- 4 -19.850523 - 0- 5- 6- 4 19.850523 - 1- 5- 0- 4 53.678778 - 1- 6- 0- 4 -53.678778 - 1- 6- 0- 5 54.977064 - 2- 3- 1- 0 0.000000 - 3- 2- 1- 0 -0.000000 - 4- 5- 0- 1 -53.651534 - 4- 6- 0- 1 53.651534 - 4- 6- 0- 5 -54.869992 - 4- 6- 5- 0 29.885677 - 4- 5- 6- 0 -29.885677 - 5- 4- 0- 1 53.626323 - 5- 6- 0- 1 -56.277112 - 5- 6- 0- 4 56.194621 - 5- 6- 4- 0 -30.558964 - 5- 4- 6- 0 31.064344 - 6- 4- 0- 1 -53.626323 - 6- 5- 0- 1 56.277112 - 6- 5- 0- 4 -56.194621 - 6- 5- 4- 0 30.558964 - 6- 4- 5- 0 -31.064344 - -Torsional angles: - - 3- 2- 1- 0 180.000000 - 6- 5- 4- 0 36.366799 - -Molecular center of mass: 0.64494926 0.00000000 2.31663792 - -Moment of inertia tensor (amu bohr^2): - 156.154091561645 0.000000000000 -52.855584120568 - 0.000000000000 199.371126996236 0.000000000000 - -52.855584120568 0.000000000000 54.459548882464 - -Principal moments of inertia (amu * bohr^2): - 31.964078 178.649562 199.371127 - -Principal moments of inertia (amu * AA^2): - 8.950855 50.026980 55.829610 - -Principal moments of inertia (g * cm^2): - 1.486325e-39 8.307181e-39 9.270731e-39 - -Molecule is an asymmetric top. - -Rotational constants (MHz): - A = 56461.542 B = 10102.130 C = 9052.169 - -Rotational constants (cm-1): - A = 1.8834 B = 0.3370 C = 0.3019 -``` diff --git a/Project#01/input/README.md b/Project#01/input/README.md deleted file mode 100644 index 839c30c..0000000 --- a/Project#01/input/README.md +++ /dev/null @@ -1 +0,0 @@ -# TEST diff --git a/Project#01/input/acetaldehyde.dat b/Project#01/input/acetaldehyde.dat deleted file mode 100644 index e005b69..0000000 --- a/Project#01/input/acetaldehyde.dat +++ /dev/null @@ -1,8 +0,0 @@ -7 -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 diff --git a/Project#01/input/allene.dat b/Project#01/input/allene.dat deleted file mode 100644 index e786d02..0000000 --- a/Project#01/input/allene.dat +++ /dev/null @@ -1,8 +0,0 @@ -7 -6 0.000000000000 0.000000000000 1.889725988579 -6 2.551130084582 0.000000000000 1.889725988579 -6 -2.551130084582 0.000000000000 1.889725988579 -1 3.495993078871 1.157216106424 0.732509882155 -1 3.495993078871 -1.157216106424 3.046942095003 -1 -3.495993078871 -1.157216106424 0.732509882155 -1 -3.495993078871 1.157216106424 3.046942095003 diff --git a/Project#01/input/benzene.dat b/Project#01/input/benzene.dat deleted file mode 100644 index b5ec7b3..0000000 --- a/Project#01/input/benzene.dat +++ /dev/null @@ -1,13 +0,0 @@ -12 -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.616448463377 -6 2.265910476936 0.000000000000 3.924672487195 -6 4.531821084796 0.000000000000 2.616448387788 -6 4.531821084796 0.000000000000 -0.000000132281 -6 2.265910689687 0.000000000000 -1.308224146651 -1 2.265910689687 -0.000000000000 -3.334218200677 -1 6.286383272575 0.000000000000 -1.012997083705 -1 6.286383239844 0.000000000000 3.629445320315 -1 2.265910476936 0.000000000000 5.950666541222 -1 -1.754562187779 0.000000000000 3.629445414801 -1 -1.754562155048 -0.000000000000 -1.012996932527 diff --git a/Project#01/output/acetaldehyde_out.txt b/Project#01/output/acetaldehyde_out.txt deleted file mode 100644 index 8ef02f9..0000000 --- a/Project#01/output/acetaldehyde_out.txt +++ /dev/null @@ -1,99 +0,0 @@ -Number of atoms: 7 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.845112131228 -8 1.899115961744 0.000000000000 4.139062527233 -1 -1.894048308506 0.000000000000 3.747688672216 -1 1.942500819960 0.000000000000 -0.701145981971 -1 -1.007295466862 -1.669971842687 -0.705916966833 -1 -1.007295466862 1.669971842687 -0.705916966833 -Interatomic distances (bohr): -1 0 2.84511 -2 0 4.55395 -2 1 2.29803 -3 0 4.19912 -3 1 2.09811 -3 2 3.81330 -4 0 2.06517 -4 1 4.04342 -4 2 4.84040 -4 3 5.87463 -5 0 2.07407 -5 1 4.05133 -5 2 5.89151 -5 3 4.83836 -5 4 3.38971 -6 0 2.07407 -6 1 4.05133 -6 2 5.89151 -6 3 4.83836 -6 4 3.38971 -6 5 3.33994 - -Bond angles: - 0- 1- 2 124.268308 - 0- 1- 3 115.479341 - 0- 4- 5 35.109529 - 0- 4- 6 35.109529 - 0- 5- 6 36.373677 - 1- 2- 3 28.377448 - 4- 5- 6 60.484476 - -Out-of-plane angles: - - 0- 3- 1- 2 -0.000000 - 0- 6- 4- 5 19.939726 - 0- 6- 5- 4 -19.850523 - 0- 5- 6- 4 19.850523 - 1- 5- 0- 4 53.678778 - 1- 6- 0- 4 -53.678778 - 1- 6- 0- 5 54.977064 - 2- 3- 1- 0 0.000000 - 3- 2- 1- 0 -0.000000 - 4- 5- 0- 1 -53.651534 - 4- 6- 0- 1 53.651534 - 4- 6- 0- 5 -54.869992 - 4- 6- 5- 0 29.885677 - 4- 5- 6- 0 -29.885677 - 5- 4- 0- 1 53.626323 - 5- 6- 0- 1 -56.277112 - 5- 6- 0- 4 56.194621 - 5- 6- 4- 0 -30.558964 - 5- 4- 6- 0 31.064344 - 6- 4- 0- 1 -53.626323 - 6- 5- 0- 1 56.277112 - 6- 5- 0- 4 -56.194621 - 6- 5- 4- 0 30.558964 - 6- 4- 5- 0 -31.064344 - -Torsional angles: - - 3- 2- 1- 0 180.000000 - 6- 5- 4- 0 36.366799 - -Molecular center of mass: 0.64494926 0.00000000 2.31663792 - -Moment of inertia tensor: - - 1 2 3 - - 1 156.1540916 0.0000000 -52.8555841 - 2 0.0000000 199.3711270 0.0000000 - 3 -52.8555841 0.0000000 54.4595489 - -Principal moments of inertia (amu * bohr^2): - 31.964078 178.649562 199.371127 - -Principal moments of inertia (amu * AA^2): - 8.950855 50.026980 55.829610 - -Principal moments of inertia (g * cm^2): - 1.486325e-39 8.307181e-39 9.270731e-39 - -Molecule is an asymmetric top. - -Rotational constants (MHz): - A = 56461.542 B = 10102.130 C = 9052.169 - -Rotational constants (cm-1): - A = 1.8834 B = 0.3370 C = 0.3019 diff --git a/Project#01/output/allene_out.txt b/Project#01/output/allene_out.txt deleted file mode 100644 index 9787cdd..0000000 --- a/Project#01/output/allene_out.txt +++ /dev/null @@ -1,154 +0,0 @@ -Number of atoms: 7 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 1.889725988579 -6 2.551130084582 0.000000000000 1.889725988579 -6 -2.551130084582 0.000000000000 1.889725988579 -1 3.495993078871 1.157216106424 0.732509882155 -1 3.495993078871 -1.157216106424 3.046942095003 -1 -3.495993078871 -1.157216106424 0.732509882155 -1 -3.495993078871 1.157216106424 3.046942095003 -Interatomic distances (bohr): -1 0 2.55113 -2 0 2.55113 -2 1 5.10226 -3 0 3.86009 -3 1 1.88973 -3 2 6.26466 -4 0 3.86009 -4 1 1.88973 -4 2 6.26466 -4 3 3.27310 -5 0 3.86009 -5 1 6.26466 -5 2 1.88973 -5 3 7.36508 -5 4 7.36508 -6 0 3.86009 -6 1 6.26466 -6 2 1.88973 -6 3 7.36508 -6 4 7.36508 -6 5 3.27310 - -Bond angles: - 0- 1- 3 120.000000 - 0- 1- 4 120.000000 - 0- 2- 5 120.000000 - 0- 2- 6 120.000000 - 0- 3- 4 64.914680 - 0- 5- 6 64.914680 - 1- 3- 4 30.000000 - 2- 5- 6 30.000000 - -Out-of-plane angles: - - 0- 4- 1- 3 -0.000000 - 0- 6- 2- 5 0.000000 - 0- 4- 3- 1 0.000000 - 0- 3- 4- 1 0.000000 - 0- 6- 5- 2 0.000000 - 0- 5- 6- 2 0.000000 - 1- 3- 0- 2 -0.000000 - 1- 4- 0- 2 0.000000 - 1- 4- 0- 3 0.000000 - 1- 5- 0- 2 0.000000 - 1- 5- 0- 3 18.315170 - 1- 5- 0- 4 -18.315170 - 1- 6- 0- 2 0.000000 - 1- 6- 0- 3 -18.315170 - 1- 6- 0- 4 18.315170 - 1- 6- 0- 5 0.000000 - 1- 4- 3- 0 0.000000 - 1- 3- 4- 0 0.000000 - 2- 3- 0- 1 0.000000 - 2- 4- 0- 1 -0.000000 - 2- 4- 0- 3 -0.000000 - 2- 5- 0- 1 0.000000 - 2- 5- 0- 3 -18.315170 - 2- 5- 0- 4 18.315170 - 2- 6- 0- 1 0.000000 - 2- 6- 0- 3 18.315170 - 2- 6- 0- 4 -18.315170 - 2- 6- 0- 5 0.000000 - 2- 6- 5- 0 0.000000 - 2- 5- 6- 0 0.000000 - 3- 2- 0- 1 0.000000 - 3- 4- 0- 1 0.000000 - 3- 4- 0- 2 0.000000 - 3- 5- 0- 1 -25.085320 - 3- 5- 0- 2 25.085320 - 3- 5- 0- 4 -34.694952 - 3- 6- 0- 1 25.085320 - 3- 6- 0- 2 -25.085320 - 3- 6- 0- 4 34.694952 - 3- 6- 0- 5 -25.085320 - 3- 4- 1- 0 0.000000 - 3- 1- 4- 0 0.000000 - 4- 2- 0- 1 0.000000 - 4- 3- 0- 1 0.000000 - 4- 3- 0- 2 0.000000 - 4- 5- 0- 1 25.085320 - 4- 5- 0- 2 -25.085320 - 4- 5- 0- 3 34.694952 - 4- 6- 0- 1 -25.085320 - 4- 6- 0- 2 25.085320 - 4- 6- 0- 3 -34.694952 - 4- 6- 0- 5 25.085320 - 4- 3- 1- 0 0.000000 - 4- 1- 3- 0 0.000000 - 5- 2- 0- 1 0.000000 - 5- 3- 0- 1 25.085320 - 5- 3- 0- 2 -25.085320 - 5- 4- 0- 1 -25.085320 - 5- 4- 0- 2 25.085320 - 5- 4- 0- 3 -25.085320 - 5- 6- 0- 1 0.000000 - 5- 6- 0- 2 0.000000 - 5- 6- 0- 3 34.694952 - 5- 6- 0- 4 -34.694952 - 5- 6- 2- 0 0.000000 - 5- 2- 6- 0 0.000000 - 6- 2- 0- 1 0.000000 - 6- 3- 0- 1 -25.085320 - 6- 3- 0- 2 25.085320 - 6- 4- 0- 1 25.085320 - 6- 4- 0- 2 -25.085320 - 6- 4- 0- 3 25.085320 - 6- 5- 0- 1 0.000000 - 6- 5- 0- 2 0.000000 - 6- 5- 0- 3 -34.694952 - 6- 5- 0- 4 34.694952 - 6- 5- 2- 0 0.000000 - 6- 2- 5- 0 0.000000 - -Torsional angles: - - 4- 3- 1- 0 180.000000 - 6- 5- 2- 0 180.000000 - -Molecular center of mass: 0.00000000 0.00000000 1.88972599 - -Moment of inertia tensor: - - 1 2 3 - - 1 10.7970237 0.0000000 0.0000000 - 2 0.0000000 210.8672829 0.0000000 - 3 0.0000000 0.0000000 210.8672829 - -Principal moments of inertia (amu * bohr^2): - 10.797024 210.867283 210.867283 - -Principal moments of inertia (amu * AA^2): - 3.023475 59.048862 59.048862 - -Principal moments of inertia (g * cm^2): - 5.020602e-40 9.805301e-39 9.805301e-39 - -Molecule is a prolate symmetric top. - -Rotational constants (MHz): - A = 167151.728 B = 8558.659 C = 8558.659 - -Rotational constants (cm-1): - A = 5.5756 B = 0.2855 C = 0.2855 diff --git a/Project#01/output/benzene_out.txt b/Project#01/output/benzene_out.txt deleted file mode 100644 index 0313cb5..0000000 --- a/Project#01/output/benzene_out.txt +++ /dev/null @@ -1,151 +0,0 @@ -Number of atoms: 12 -Input Cartesian coordinates: -6 0.000000000000 0.000000000000 0.000000000000 -6 0.000000000000 0.000000000000 2.616448463377 -6 2.265910476936 0.000000000000 3.924672487195 -6 4.531821084796 0.000000000000 2.616448387788 -6 4.531821084796 0.000000000000 -0.000000132281 -6 2.265910689687 0.000000000000 -1.308224146651 -1 2.265910689687 -0.000000000000 -3.334218200677 -1 6.286383272575 0.000000000000 -1.012997083705 -1 6.286383239844 0.000000000000 3.629445320315 -1 2.265910476936 0.000000000000 5.950666541222 -1 -1.754562187779 0.000000000000 3.629445414801 -1 -1.754562155048 -0.000000000000 -1.012996932527 -Interatomic distances (bohr): -1 0 2.61645 -2 0 4.53182 -2 1 2.61645 -3 0 5.23290 -3 1 4.53182 -3 2 2.61645 -4 0 4.53182 -4 1 5.23290 -4 2 4.53182 -4 3 2.61645 -5 0 2.61645 -5 1 4.53182 -5 2 5.23290 -5 3 4.53182 -5 4 2.61645 -6 0 4.03130 -6 1 6.36748 -6 2 7.25889 -6 3 6.36748 -6 4 4.03130 -6 5 2.02599 -7 0 6.36748 -7 1 7.25889 -7 2 6.36748 -7 3 4.03130 -7 4 2.02599 -7 5 4.03130 -7 6 4.64244 -8 0 7.25889 -8 1 6.36748 -8 2 4.03130 -8 3 2.02599 -8 4 4.03130 -8 5 6.36748 -8 6 8.04095 -8 7 4.64244 -9 0 6.36748 -9 1 4.03130 -9 2 2.02599 -9 3 4.03130 -9 4 6.36748 -9 5 7.25889 -9 6 9.28488 -9 7 8.04095 -9 8 4.64244 -10 0 4.03130 -10 1 2.02599 -10 2 4.03130 -10 3 6.36748 -10 4 7.25889 -10 5 6.36748 -10 6 8.04095 -10 7 9.28488 -10 8 8.04095 -10 9 4.64244 -11 0 2.02599 -11 1 4.03130 -11 2 6.36748 -11 3 7.25889 -11 4 6.36748 -11 5 4.03130 -11 6 4.64244 -11 7 8.04095 -11 8 9.28488 -11 9 8.04095 -11 10 4.64244 - -Bond angles: - 0- 1- 2 120.000000 - 0- 1-10 120.000000 - 0- 5- 6 120.000000 - 1- 2- 3 120.000000 - 1- 2- 9 120.000000 - 2- 3- 4 120.000000 - 2- 3- 8 120.000000 - 3- 4- 5 120.000001 - 3- 4- 7 120.000000 - 4- 5- 6 120.000001 - -Out-of-plane angles: - - 0-10- 1- 2 -0.000000 - 0- 6- 5- 4 0.000000 - 1-11- 0- 5 0.000000 - 1- 9- 2- 3 -0.000000 - 2-10- 1- 0 0.000000 - 2- 8- 3- 4 -0.000000 - 3- 9- 2- 1 0.000000 - 3- 7- 4- 5 -0.000000 - 4- 8- 3- 2 0.000000 - 4- 6- 5- 0 0.000000 - 5-11- 0- 1 -0.000000 - 5- 7- 4- 3 0.000000 - 6- 4- 5- 0 0.000000 - 7- 5- 4- 3 -0.000000 - 8- 4- 3- 2 0.000000 - 9- 3- 2- 1 -0.000000 -10- 2- 1- 0 -0.000000 -11- 5- 0- 1 0.000000 - -Torsional angles: - - 3- 2- 1- 0 0.000001 - 4- 3- 2- 1 0.000002 - 5- 4- 3- 2 0.000002 - 6- 5- 4- 3 179.999999 - 7- 4- 3- 2 179.999998 - 8- 3- 2- 1 179.999998 - 9- 2- 1- 0 180.000000 - -Molecular center of mass: 2.26591056 0.00000000 1.30822418 - -Moment of inertia tensor: - - 1 2 3 - - 1 311.6116287 0.0000000 -0.0000145 - 2 0.0000000 623.2231997 0.0000000 - 3 -0.0000145 0.0000000 311.6115710 - -Principal moments of inertia (amu * bohr^2): - 311.611568 311.611632 623.223200 - -Principal moments of inertia (amu * AA^2): - 87.260139 87.260157 174.520296 - -Principal moments of inertia (g * cm^2): - 1.448990e-38 1.448990e-38 2.897980e-38 - -Molecule is an oblate symmetric top. - -Rotational constants (MHz): - A = 5791.637 B = 5791.636 C = 2895.818 - -Rotational constants (cm-1): - A = 0.1932 B = 0.1932 C = 0.0966 diff --git a/Project#01/project1-instructions.pdf b/Project#01/project1-instructions.pdf deleted file mode 100644 index e7a7e5748c1616ac74f9a3bbf92fdb471622f4b6..0000000000000000000000000000000000000000 GIT binary patch literal 0 HcmV?d00001 literal 71749 zcmb5V1wd8J^8gA+Nr$A8f`G)OySqCDBrkBOONVqLUD8t0jYy}YbVzqdOGr2G0{VUa z>%HFt<(%C!vokw8Gdp``4yB@~I6V^sD-sJSBPrO>oRpUr2_Or!Hgzx~W#(ezB7OKl z0*Hew9e{SE0C7tL2cRg>2y6^Q;^#-Qcd!E*SRuL0>}t!zKCi)S-Y-jhsfCN#NMcu@ zT=633XW@%tOXX-w5|g^hhL_PSqcO+Q7bhSTMiKof_n+-O#O`nG;AaJ$y*6*_p*@{F zPxClpaKf;=6JHOOA-y8X3~OjZ6slEi$bmCs^lD}22>N7{xgZ=1^ z8ri$f?CvsK+UGdWzDDluHP2q;I9=Rc)6#lWR`ibT=H$AYk&RNEYhF$c$2Rq|VHbt1 za;^3DJ~%H#9omQ4q9Ut@n#rKpt2C)w%u z?z(I{uM6$i;D}~sJxlr&Qrs^Dtn_zNfbL!@^gH7joSz&H$r~?BRqoi=%$4U$w;frf 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[here](./input/h2o_hessian.txt) for the H2O test case. -The first integer in the file is the number of atoms (which you should compare to the corresponding value from the geometry file as a test of consistency), -while the remaining values have the following format: - - - - * [Hint 1](./hints/hint1.md): Reading the Hessian - -## Step 3: Mass-Weight the Hessian Matrix - -Divide each element of the Hessian matrix by the product of square-roots of the masses of the atoms associated with the given coordinates: - - - -where mi represents the mass of the atom corresponding to atom *i*. Use atomic mass units (amu) for the masses, just as -for [Project #1](../Project%2301). - - * [Hint 2](./hints/hint2.md): Solution - -## Step 4: Diagonalize the Mass-Weighted Hessian Matrix - -Compute the eigenvalues of the mass-weighted Hessian: - - - -You should consider using the same canned diagonalization function -you used in [Project #1](../Project%2301). - - * [Hint 3](./hints/hint3.md): Solution - -## Step 5: Compute the Harmonic Vibrational Frequencies - -The vibrational frequencies are proportional to the squareroot of the eigenvalues of the mass-weighted Hessian: - - - -The most common units to use for vibrational frequencies is cm-1. - - * [Hint 4](./hints/hint4.md): Solution - -## Reference -E.B. Willson, J.C. Decius, and P.C. Cross, __Molecular Vibrations__, McGraw-Hill, 1955. - -## Test Cases - - * Water: [Coordinates](./input/h2o_geom.txt) - | [Hessian](./input/h2o_hessian.txt) - | [Output](./output/h2o_vib_out.txt) (see the note at the bottom of [Hint 4](./hints/hint4.md)) - * Benzene: [Coordinates](./input/benzene_geom.txt) - | [Hessian](./input/benzene_hessian.txt) - | [Output](./output/benzene_vib_out.txt) - * 3-chloro-1-butene: [Coordinates](./input/3c1b_geom.txt) - | [Hessian](./input/3c1b_hessian.txt) - | [Output](./output/3c1b_vib_out.txt) diff --git a/Project#02/figures/.DS_Store b/Project#02/figures/.DS_Store deleted file mode 100644 index cbaa184433029da3e149ca73efb64d2c593dc823..0000000000000000000000000000000000000000 GIT binary patch literal 0 HcmV?d00001 literal 6148 zcmeHKK~BRk5S%SVDk_KGfD7^mg2WG^sz`9=$^k-3iWCTx0@pl;_wWe50kgJMXwsaJ zP=$7@^{m(4b#`3EF#s7q=f}VZz<{dQ+hMatbX>J1z3AB{iqDbY4p(^MFKNv-$0jnM zdv}N&x7@dayY{_*ub9$XV1@;)oMSVh?yb(f#}OXb7H4I3ot0I_Jo+a(r6!+VXaReT 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zmQH7kpqHXaWwW=7yXmx=zp8t823O&~4*v9%cV))f5ZgI@LN&$&B8>X7Wqgo8!@C$53hc+viO=XJ{72W9D=;)!u0dYyQ65PH4SzN1#(b z7=2LSUwE)%@n5eFfJOwEroL^P^E%mD3GK_ackHIePQxq@)94nx1?bBpJ)QaBLfRaP z*5S4`un~9ab|(I-e{OW?#s@9?2dL=$YTew^PyW@P6`kZ?C;esJqp%)z(Je1ygsXCD zH2emM`Mnum zc#^7+JtxxDy7@Od7R>ehYr)AIJ6F0~}{)LAgqa{ZN8S~Kr3 zsLhuy+lFo^p|sZAzmOQ;#@?6Tav=4Qj*<4J`nMGx6hrfgs%rNo)_YdEjaL7 zO@8ja+N>r8KPtCpqT0zeyKlf@=o@sc)M=hDPvCe;^uo11wv{or($=& zSQqfcW5UAI7s{5bwB2$u?W1n!Apng#Q`QuHT;ufW;#Zd+#+sQ8i;j97_ndw*=kE~m zA3RKYf5yVAumsUVS;?PeKehc5aMU^T*|S$8qDMaOY$3tD)q59Vj-Xw?dp`GT%WaQ} zoI?V_^HDz8E)!Sm+&FrJHGiYkda$~5tU-A=dt%14^#2O test case, the 9×9 mass-weighted Hessian is: -``` - 1 2 3 4 5 6 7 8 9 - - 1 0.0057996 0.0000000 0.0000000 -0.0115523 0.0000000 0.0000000 -0.0115523 0.0000000 0.0000000 - 2 0.0000000 0.0198271 0.0000000 0.0000000 -0.0394937 0.0199304 0.0000000 -0.0394937 -0.0199304 - 3 0.0000000 0.0000000 0.0175112 0.0000000 0.0086617 -0.0348807 0.0000000 -0.0086617 -0.0348807 - 4 -0.0115523 0.0000000 0.0000000 0.0510672 0.0000000 0.0000000 -0.0050452 0.0000000 0.0000000 - 5 0.0000000 -0.0394937 0.0086617 0.0000000 0.1716643 -0.0569527 0.0000000 -0.0143291 0.0224462 - 6 0.0000000 0.0199304 -0.0348807 0.0000000 -0.0569527 0.1258526 0.0000000 -0.0224462 0.0131055 - 7 -0.0115523 0.0000000 0.0000000 -0.0050452 0.0000000 0.0000000 0.0510672 0.0000000 0.0000000 - 8 0.0000000 -0.0394937 -0.0086617 0.0000000 -0.0143291 -0.0224462 0.0000000 0.1716643 0.0569527 - 9 0.0000000 -0.0199304 -0.0348807 0.0000000 0.0224462 0.0131055 0.0000000 0.0569527 0.1258526 -``` diff --git a/Project#02/hints/hint3.md b/Project#02/hints/hint3.md deleted file mode 100644 index 7440aa9..0000000 --- a/Project#02/hints/hint3.md +++ /dev/null @@ -1,12 +0,0 @@ -The eigenvalues of the mass-weighted Hessian for the H2O test case (in atomic units) are: -``` - 8 0.2351542439 - 7 0.2107113210 - 6 0.1317512832 - 5 0.0561123974 - 4 0.0547551476 - 3 0.0518216614 - 2 0.0000000000 - 1 0.0000000000 - 0 0.0000000000 -``` diff --git a/Project#02/hints/hint4.md b/Project#02/hints/hint4.md deleted file mode 100644 index ff7a389..0000000 --- a/Project#02/hints/hint4.md +++ /dev/null @@ -1,13 +0,0 @@ -The harmonic vibrational frequencies for the H2O test case (in cm-1) are: -``` - 8 2492.7600 - 7 2359.6522 - 6 1865.8704 - 5 1217.6808 - 4 1202.8640 - 3 1170.1990 - 2 0.0210 - 1 0.0000 - 0 0.0000 -``` -Note that there are only three zero frequencies in this case when there should be six. This is because the structure used in the computation is not a stationary point on the potential energy surface, and thus the three “rotational frequencies” are non-zero. diff --git a/Project#02/input/3c1b_geom.txt b/Project#02/input/3c1b_geom.txt deleted file mode 100644 index 5807948..0000000 --- a/Project#02/input/3c1b_geom.txt +++ /dev/null @@ -1,13 +0,0 @@ -12 - 6.0000000000 0.1690059610 3.1233433100 -0.3345553720 - 6.0000000000 -0.0386421959 0.4206229820 0.7520430680 - 6.0000000000 2.0569045600 -1.3758742600 -0.1486055380 - 6.0000000000 4.4719971000 -0.8585641720 -0.0315570842 - 1.0000000000 5.1968623000 0.9074367080 0.6974099730 - 1.0000000000 -1.3822808500 4.2799539600 0.3473315670 - 1.0000000000 5.8762121500 -2.2019961400 -0.6625964520 - 1.0000000000 1.4102155500 -3.1763622600 -0.8785797820 - 1.0000000000 -0.0505049904 0.5084677190 2.8179601800 - 1.0000000000 0.1191743850 3.0814658800 -2.3848397600 - 1.0000000000 1.9378539900 3.9710910300 0.2692445360 - 17.0000000000 -3.1213603000 -0.8957190610 -0.0958753352 diff --git a/Project#02/input/3c1b_hessian.txt b/Project#02/input/3c1b_hessian.txt deleted file mode 100644 index d76214b..0000000 --- a/Project#02/input/3c1b_hessian.txt +++ /dev/null @@ -1,433 +0,0 @@ - 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0.0000000000 -0.0800202030 -0.1400453646 - 0.0000000000 0.0226218083 0.0132080159 - 0.0000000000 0.0573983947 0.1268373488 diff --git a/Project#02/output/3c1b_vib_out.txt b/Project#02/output/3c1b_vib_out.txt deleted file mode 100644 index 7280401..0000000 --- a/Project#02/output/3c1b_vib_out.txt +++ /dev/null @@ -1,76 +0,0 @@ - -Hessian eigenvalues (hartree/amu-bohr^2): - 35 0.5504194388 - 34 0.5372530704 - 33 0.5351184811 - 32 0.5255730312 - 31 0.5062966607 - 30 0.4992575932 - 29 0.4845191221 - 28 0.1594678267 - 27 0.1246207278 - 26 0.1240628138 - 25 0.1124389759 - 24 0.1102183592 - 23 0.0940432225 - 22 0.0897847299 - 21 0.0836000497 - 20 0.0690595364 - 19 0.0640720123 - 18 0.0595822760 - 17 0.0569922250 - 16 0.0512084824 - 15 0.0498908695 - 14 0.0410337099 - 13 0.0283830220 - 12 0.0213722484 - 11 0.0088837125 - 10 0.0065288923 - 9 0.0046443780 - 8 0.0028070052 - 7 0.0022837821 - 6 0.0000001155 - 5 0.0000000871 - 4 0.0000000051 - 3 0.0000000000 - 2 0.0000000000 - 1 0.0000000000 - 0 -0.0004144295 - -Harmonic vibrational frequencies (cm^-1): - 35 3813.7387 - 34 3767.8491 - 33 3760.3566 - 32 3726.6670 - 31 3657.6874 - 30 3632.1719 - 29 3578.1580 - 28 2052.7714 - 27 1814.6764 - 26 1810.6098 - 25 1723.7032 - 24 1706.5972 - 23 1576.4050 - 22 1540.2999 - 21 1486.3029 - 20 1350.8772 - 19 1301.1826 - 18 1254.7656 - 17 1227.1901 - 16 1163.2552 - 15 1148.1922 - 14 1041.2966 - 13 866.0309 - 12 751.5003 - 11 484.5084 - 10 415.3592 - 9 350.3223 - 8 272.3489 - 7 245.6583 - 6 1.7468 - 5 1.5170 - 4 0.3667 - 3 0.0305 - 2 0.0290 - 1 0.0099 - 0 104.6476i diff --git a/Project#02/output/benzene_vib_out.txt b/Project#02/output/benzene_vib_out.txt deleted file mode 100644 index de0cdc3..0000000 --- a/Project#02/output/benzene_vib_out.txt +++ /dev/null @@ -1,76 +0,0 @@ - -Hessian eigenvalues (hartree/amu-bohr^2): - 35 0.5314353702 - 34 0.5283614298 - 33 0.5283614298 - 32 0.5244972742 - 31 0.5244972740 - 30 0.5193180123 - 29 0.1413237674 - 28 0.1413237674 - 27 0.1189063721 - 26 0.1189063720 - 25 0.0963092312 - 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David Sherrill. -A concise set of instructions for this project may be found [here](./project3-instructions.pdf). - -We thank Dr. Yukio Yamaguchi of the University of Georgia for the original version of this project. - -The test case used in the following discussion is for a water molecule with a bond-length of 1.1 Å -and a bond angle of 104.0o with an STO-3G basis set. The input to the project consists of the -[nuclear repulsion energy](./input/h2o/STO-3G/enuc.dat) - and pre-computed sets of one- and two-electron integrals: -[overlap integrals](./input/h2o/STO-3G/s.dat), -[kinetic-energy integrals](./input/h2o/STO-3G/t.dat), -[nuclear-attraction integrals](./input/h2o/STO-3G/v.dat), -[electron-electron repulsion integrals](./input/h2o/STO-3G/eri.dat). - - -## Step 1: Nuclear Repulsion Energy - -Read the nuclear repulsion energy from the [enuc.dat](./input/h2o/STO-3G/enuc.dat) - -## Step 2: One-Electron Integrals - -Read the AO-basis [overlap](./input/h2o/STO-3G/s.dat) - - - -[kinetic-energy](./input/h2o/STO-3G/t.dat) - - - -[nuclear-attraction integrals](./input/h2o/STO-3G/v.dat) - - - -and store them in appropriately constructed matrices. Then form the "core Hamiltonian": - - - -Note that the one-electron integrals provided include only the *permutationally unique* integrals, but you should store the full matrices for convenience. -Note also that the AO indices on the integrals in the files start with "1" rather than "0". - - * [Hint 1](./hints/hint2-1.md): Core Hamiltonian - -## Step #3: Two-Electron Integrals - -Read the two-electron repulsion integrals from the -[eri.dat](./input/h2o/STO-3G/eri.dat) -file. -The integrals in this file are provided in Mulliken notation over real AO basis functions: - - - -Hence, the integrals obey the eight-fold permutational symmetry relationships: - - - -and only the permutationally unique integrals are provided in the file, with the restriction that, for each integral, the following relationships hold: - - - -where - - - -Note that the two-electron integrals may be stored efficiently in a one-dimensional array and the above relationship used to map between given -μ, ν, λ, and σ indices and a "compound index" defined as: - - - - * [Hint 1](./hints/hint3-1.md): Compound indices - * [Hint 2](./hints/hint3-2.md): Pre-Computed Lookup Arrays - * [Hint 3](./hints/hint3-3.md): Reading the two-electron integrals - - -## Step 4: Build the Orthogonalization Matrix - -Diagonalize the overlap matrix: - - - -where LS is the matrix of eigenvectors (columns) and ΛS is the diagonal matrix of corresponding eigenvalues. - -Build the symmetric orthogonalization matrix using: - - - -where the tilde denotes the matrix transpose. - - * [Hint 1](./hints/hint4-1.md): S-1/2 Matrix - - -## Step 5: Build the Initial Guess Density - -Form an initial (guess) Fock matrix in the orthonormal AO basis using the core Hamiltonian as a guess: - - - -Diagonalize the Fock matrix: - - - -Note that the ε0 matrix contains the initial orbital energies. - -Transform the eigenvectors into the original (non-orthogonal) AO basis: - - - -Build the density matrix using the occupied MOs: - - - -where *m* indexes the columns of the coefficient matrices, and the summation includes only the occupied spatial MOs. - - * [Hint 1](./hints/hint5-1.md): Transformed Fock matrix - * [Hint 2](./hints/hint5-2.md): Initial MO Coefficients - * [Hint 3](./hints/hint5-3.md): Initial Density Matrix - -## Step 6: Compute the Inital SCF Energy - -The SCF electronic energy may be computed using the density matrix as: - - - -The total energy is the sum of the electronic energy and the nuclear repulsion energy: - - - -where *0* denotes the initial SCF energy. - - * [Hint 1](./hints/hint6-1.md): Initial Electronic Energy - -## Step #7: Compute the New Fock Matrix - -Start the SCF iterative procedure by building a new Fock matrix using the previous iteration's density as: - - - -where the double-summation runs over all the AOs and *i-1* denotes the density for the last iteration. - - * [Hint 1](./hints/hint7-1.md): New Fock Matrix - * [Hint 2](./hints/hint7-2.md): Fock-Build Code - -## Step #8: Build the New Density Matrix - -Form the new density matrix following the same procedure as in Step #5 above: - -Orthogonalize: - - - -Diagonalize: - - - -Back-transform: - - - -Compute the density: - - - -where *i* denotes the current iteration density. - -## Step #9: Compute the New SCF Energy - -Compute the new SCF energy as before: - - - -where *i* denotes the SCF energy for the *i*th iteration. - -## Step #10: Test for Convergence -Test both the energy and the density for convergence: - - - -If the difference in consecutive SCF energy and the root-mean-squared difference in consecutive densities do not fall below the prescribed thresholds, return to Step #7 and continue from there. - - * [Hint 1](./hints/hint10-1.md): Energies for Each Iteration - -## Additional Concepts -### The MO-Basis Fock Matrix -At convergence, the canonical Hartree-Fock MOs are, by definition, eigenfunctions of the Fock operator, viz. - - - -If we multiply on the left by an arbitrary MO and integrate, we obtain: - - - -In other words, the Fock matrix should be diagonal in the MO basis, with the orbital energies as its diagonal elements. We can demonstrate this explicitly using the AO-basis Fock matrix by first re-writing the above expression using the LCAO-MO coefficients: - - - -Use the above equation to transform the Fock matrix from the AO basis to the MO basis and demonstrate that it is indeed diagonal (to within the convergence limits of the SCF iterative procedure). - -### One-Electron Properties -As discussed in detail in Ch. 3 of the text by Szabo and Ostlund, the calculation of one-electron properties requires density matrix and the relevant property integrals. The electronic contribution to the electric-dipole moment may be computed using, - - - -where the vector notation implies three sets of dipole-moment integrals -- one for each Cartesian component of the dipole operator. - -Two points to note: - - In order to compute the total dipole moment, you must include the nuclear contribution, which requires the atomic numbers and Cartesian coordinates of the nuclei, in addition to the above. - - The factor 2 appearing above arises because the definition of the density used in this project differs from that used in Szabo & Ostlund. - -The test cases provided below include the structural information dipole integrals needed to compute the dipole moment. - -### Population Analysis/Atomic Charges -A Mulliken population analysis (also described in Szabo & Ostlund, Ch. 3) requires the overlap integrals and the electron density, in addition to information about the number of basis functions centered on each atom. The charge on atom *A* may be computed as: - - - -where the summation is limited to only those basis functions centered on atom *A*. - -## Test Cases - * STO-3G Water: [Geometry](./input/h2o/STO-3G/geom.dat) | [Enuc](./input/h2o/STO-3G/enuc.dat) | [S](./input/h2o/STO-3G/s.dat) | [T](./input/h2o/STO-3G/t.dat) | [V](./input/h2o/STO-3G/v.dat) | [ERI](./input/h2o/STO-3G/eri.dat) | [Mu_X](./input/h2o/STO-3G/mux.dat) | [Mu_Y](./input/h2o/STO-3G/muy.dat) | [Mu_Z](./input/h2o/STO-3G/muz.dat) | [output](./output/h2o/STO-3G/output.txt) - * DZ Water: [Geometry](./input/h2o/DZ/geom.dat) | [Enuc](./input/h2o/DZ/enuc.dat) | [S](./input/h2o/DZ/s.dat) | [T](./input/h2o/DZ/t.dat) | [V](./input/h2o/DZ/v.dat) | [ERI](./input/h2o/DZ/eri.dat) | [Mu_X](./input/h2o/DZ/mux.dat) | [Mu_Y](./input/h2o/DZ/muy.dat) | [Mu_Z](./input/h2o/DZ/muz.dat) | [output](./output/h2o/DZ/output.txt) - * DZP Water: [Geometry](./input/h2o/DZP/geom.dat) | [Enuc](./input/h2o/DZP/enuc.dat) | [S](./input/h2o/DZP/s.dat) | [T](./input/h2o/DZP/t.dat) | [V](./input/h2o/DZP/v.dat) | [ERI](./input/h2o/DZP/eri.dat) | [Mu_X](./input/h2o/DZP/mux.dat) | [Mu_Y](./input/h2o/DZP/muy.dat) | [Mu_Z](./input/h2o/DZP/muz.dat) | [output](./output/h2o/DZP/output.txt) - * STO-3G Methane: [Geometry](./input/ch4/STO-3G/geom.dat) | [Enuc](./input/ch4/STO-3G/enuc.dat) | [S](./input/ch4/STO-3G/s.dat) | [T](./input/ch4/STO-3G/t.dat) | [V](./input/ch4/STO-3G/v.dat) | [ERI](./input/ch4/STO-3G/eri.dat) | [Mu_X](./input/ch4/STO-3G/mux.dat) | [Mu_Y](./input/ch4/STO-3G/muy.dat) | [Mu_Z](./input/ch4/STO-3G/muz.dat) | [output](./output/ch4/STO-3G/output.txt) diff --git a/Project#03/figures/atomic-charge.png b/Project#03/figures/atomic-charge.png deleted file mode 100644 index 444285162d2e57b73e67428abacbfab2a8e6fc6a..0000000000000000000000000000000000000000 GIT binary patch literal 0 HcmV?d00001 literal 7319 zcmb_hc|6qbx1Y376iLhXi|k8Hj4{K^*k>`enK1@4MoD8fW6X@%$7FBym1IkcXcNj( 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0.071369905102345 - 9 9 7 5 0.115242183476134 - 9 7 9 3 -0.023364154750318 - 9 7 9 4 -0.023364154750318 - 9 7 9 5 0.029743802645650 - 9 9 7 6 0.055912476950067 - 9 7 9 6 0.012847889010515 - 9 9 7 7 0.296353939081569 - 9 7 9 7 0.015770501299918 - 9 9 8 1 0.029275118256461 - 9 8 9 1 0.006478426740226 - 9 9 8 2 0.181078653129682 - 9 8 9 2 0.044234528245132 - 9 9 8 3 -0.115242183476134 - 9 9 8 4 0.071369905102345 - 9 9 8 5 -0.071369905102345 - 9 8 9 3 -0.029743802645650 - 9 8 9 4 -0.023364154750318 - 9 8 9 5 0.023364154750318 - 9 9 8 6 0.055912476950067 - 9 8 9 6 0.012847889010515 - 9 9 8 7 0.055912476950067 - 9 8 9 7 0.012847889010515 - 9 9 8 8 0.296353939081570 - 9 8 9 8 0.015770501299918 - 9 9 9 1 0.031703797879678 - 9 9 9 2 0.304981529941436 - 9 9 9 3 -0.206879432071914 - 9 9 9 4 -0.206879432071914 - 9 9 9 5 0.206879432071914 - 9 9 9 6 0.085276746780538 - 9 9 9 7 0.085276746780538 - 9 9 9 8 0.085276746780538 - 9 9 9 9 0.774605895725855 diff --git a/Project#03/fortran/geom.dat b/Project#03/fortran/geom.dat deleted file mode 100644 index 9c536a9..0000000 --- a/Project#03/fortran/geom.dat +++ /dev/null @@ -1,6 +0,0 @@ -5 -6.000000000000 -0.000000000000 0.000000000000 0.000000000000 -1.000000000000 1.183771681898 -1.183771681898 -1.183771681898 -1.000000000000 1.183771681898 1.183771681898 1.183771681898 -1.000000000000 -1.183771681898 1.183771681898 -1.183771681898 -1.000000000000 -1.183771681898 -1.183771681898 1.183771681898 diff --git a/Project#03/fortran/input.dat b/Project#03/fortran/input.dat deleted file mode 100644 index 6dfb483..0000000 --- a/Project#03/fortran/input.dat +++ /dev/null @@ -1,43 +0,0 @@ -psi: ( - label = "CH4 SCF Test Case" - wfn = scf - jobtype = oeprop - reference = rhf - basis = "STO-3G" - units = angstrom - subgroup = c1 - delete_tei = false - delete_oei = false - zmat = ( - C - H 1 r - H 1 r 2 td - H 1 r 2 td 3 d - H 1 r 2 td 4 d - ) - zvars = ( - r 1.085 - td 109.47122063449069136958 - d 120.0 - ) -) - -basis: ( - carbon: "STO-3G" = - ( (S ( 71.61683730 0.15432900) - ( 13.04509630 0.53532810) - ( 3.53051220 0.44463450) ) - (S ( 2.94124940 -0.09996720) - ( 0.68348310 0.39951280) - ( 0.22228990 0.70011550) ) - (P ( 2.94124940 0.15591630) - ( 0.68348310 0.60768370) - ( 0.22228990 0.39195740) ) - ) - - hydrogen: "STO-3G"= - ( (S ( 3.42525090 0.15432890) - ( 0.62391370 0.53532810) - ( 0.16885540 0.44463450) ) - ) -) diff --git a/Project#03/fortran/mux.dat b/Project#03/fortran/mux.dat deleted file mode 100644 index 9dca8dd..0000000 --- a/Project#03/fortran/mux.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 0.000000000000000 - 2 1 0.000000000000000 - 2 2 0.000000000000000 - 3 1 -0.071855488532817 - 3 2 -0.838743574800986 - 3 3 0.000000000000000 - 4 1 -0.000000000000000 - 4 2 0.000000000000000 - 4 3 -0.000000000000000 - 4 4 0.000000000000000 - 5 1 0.000000000000000 - 5 2 0.000000000000000 - 5 3 -0.000000000000000 - 5 4 0.000000000000000 - 5 5 0.000000000000000 - 6 1 -0.004780775261548 - 6 2 -0.306592476518555 - 6 3 -0.519567036508228 - 6 4 0.163831354490276 - 6 5 0.163831354490276 - 6 6 -1.183771681897730 - 7 1 -0.004780775261548 - 7 2 -0.306592476518555 - 7 3 -0.519567036508228 - 7 4 -0.163831354490276 - 7 5 -0.163831354490276 - 7 6 -0.202918556316052 - 7 7 -1.183771681897730 - 8 1 0.004780775261548 - 8 2 0.306592476518555 - 8 3 -0.519567036508228 - 8 4 0.163831354490276 - 8 5 -0.163831354490276 - 8 6 -0.000000000000000 - 8 7 -0.000000000000000 - 8 8 1.183771681897730 - 9 1 0.004780775261548 - 9 2 0.306592476518555 - 9 3 -0.519567036508228 - 9 4 -0.163831354490276 - 9 5 0.163831354490276 - 9 6 0.000000000000000 - 9 7 0.000000000000000 - 9 8 0.202918556316052 - 9 9 1.183771681897731 diff --git a/Project#03/fortran/muy.dat b/Project#03/fortran/muy.dat deleted file mode 100644 index 3b70d58..0000000 --- a/Project#03/fortran/muy.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 -0.000000000000000 - 2 1 -0.000000000000000 - 2 2 -0.000000000000000 - 3 1 -0.000000000000000 - 3 2 0.000000000000000 - 3 3 -0.000000000000000 - 4 1 -0.071855488532817 - 4 2 -0.838743574800986 - 4 3 0.000000000000000 - 4 4 -0.000000000000000 - 5 1 -0.000000000000000 - 5 2 -0.000000000000000 - 5 3 0.000000000000000 - 5 4 -0.000000000000000 - 5 5 -0.000000000000000 - 6 1 0.004780775261548 - 6 2 0.306592476518555 - 6 3 0.163831354490276 - 6 4 -0.519567036508228 - 6 5 -0.163831354490276 - 6 6 1.183771681897730 - 7 1 -0.004780775261548 - 7 2 -0.306592476518555 - 7 3 -0.163831354490276 - 7 4 -0.519567036508228 - 7 5 -0.163831354490276 - 7 6 -0.000000000000000 - 7 7 -1.183771681897730 - 8 1 -0.004780775261548 - 8 2 -0.306592476518555 - 8 3 0.163831354490276 - 8 4 -0.519567036508228 - 8 5 0.163831354490276 - 8 6 -0.000000000000000 - 8 7 -0.202918556316052 - 8 8 -1.183771681897730 - 9 1 0.004780775261548 - 9 2 0.306592476518555 - 9 3 -0.163831354490276 - 9 4 -0.519567036508228 - 9 5 0.163831354490276 - 9 6 0.202918556316052 - 9 7 0.000000000000000 - 9 8 0.000000000000000 - 9 9 1.183771681897731 diff --git a/Project#03/fortran/muz.dat b/Project#03/fortran/muz.dat deleted file mode 100644 index 5e85ca2..0000000 --- a/Project#03/fortran/muz.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 -0.000000000000000 - 2 1 -0.000000000000000 - 2 2 -0.000000000000000 - 3 1 -0.000000000000000 - 3 2 0.000000000000000 - 3 3 -0.000000000000000 - 4 1 0.000000000000000 - 4 2 -0.000000000000000 - 4 3 0.000000000000000 - 4 4 -0.000000000000000 - 5 1 -0.071855488532817 - 5 2 -0.838743574800986 - 5 3 0.000000000000000 - 5 4 -0.000000000000000 - 5 5 -0.000000000000000 - 6 1 0.004780775261548 - 6 2 0.306592476518555 - 6 3 0.163831354490276 - 6 4 -0.163831354490276 - 6 5 -0.519567036508228 - 6 6 1.183771681897730 - 7 1 -0.004780775261548 - 7 2 -0.306592476518555 - 7 3 -0.163831354490276 - 7 4 -0.163831354490276 - 7 5 -0.519567036508228 - 7 6 0.000000000000000 - 7 7 -1.183771681897730 - 8 1 0.004780775261548 - 8 2 0.306592476518555 - 8 3 -0.163831354490276 - 8 4 0.163831354490276 - 8 5 -0.519567036508228 - 8 6 0.202918556316052 - 8 7 0.000000000000000 - 8 8 1.183771681897730 - 9 1 -0.004780775261548 - 9 2 -0.306592476518554 - 9 3 0.163831354490276 - 9 4 0.163831354490276 - 9 5 -0.519567036508228 - 9 6 0.000000000000000 - 9 7 -0.202918556316052 - 9 8 0.000000000000000 - 9 9 -1.183771681897729 diff --git a/Project#03/fortran/s.dat b/Project#03/fortran/s.dat deleted file mode 100644 index cfa1ff6..0000000 --- a/Project#03/fortran/s.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 1.000000000000000 - 2 1 0.248362397956661 - 2 2 1.000000000000000 - 3 1 0.000000000000000 - 3 2 0.000000000000000 - 3 3 0.999999999999999 - 4 1 -0.000000000000000 - 4 2 0.000000000000000 - 4 3 0.000000000000000 - 4 4 0.999999999999999 - 5 1 0.000000000000000 - 5 2 0.000000000000000 - 5 3 0.000000000000000 - 5 4 0.000000000000000 - 5 5 0.999999999999999 - 6 1 0.063006775327623 - 6 2 0.493634843691260 - 6 3 0.270769041240711 - 6 4 -0.270769041240711 - 6 5 -0.270769041240711 - 6 6 1.000000000000000 - 7 1 0.063006775327623 - 7 2 0.493634843691260 - 7 3 0.270769041240711 - 7 4 0.270769041240711 - 7 5 0.270769041240711 - 7 6 0.171416971210824 - 7 7 1.000000000000000 - 8 1 0.063006775327623 - 8 2 0.493634843691261 - 8 3 -0.270769041240711 - 8 4 0.270769041240711 - 8 5 -0.270769041240711 - 8 6 0.171416971210824 - 8 7 0.171416971210824 - 8 8 1.000000000000000 - 9 1 0.063006775327623 - 9 2 0.493634843691260 - 9 3 -0.270769041240711 - 9 4 -0.270769041240711 - 9 5 0.270769041240711 - 9 6 0.171416971210824 - 9 7 0.171416971210824 - 9 8 0.171416971210824 - 9 9 1.000000000000000 diff --git a/Project#03/fortran/src/const.F90 b/Project#03/fortran/src/const.F90 deleted file mode 100644 index fca71a3..0000000 --- a/Project#03/fortran/src/const.F90 +++ /dev/null @@ -1,21 +0,0 @@ -module const - use, intrinsic :: iso_c_binding, only: c_int32_t, c_int64_t - - implicit none - - ! Integer types - integer, parameter :: int_32 = selected_int_kind(6) - integer, parameter :: int_64 = selected_int_kind(15) - - ! Real types - integer, parameter :: sp = selected_real_kind(6,37) - integer, parameter :: dp = selected_real_kind(15,307) - - integer, parameter :: p = dp - - ! Highest precision pi - real(p), parameter :: pi = 4.0_p * atan(1.0_p) - - real(p), parameter :: depsilon = 1.e-12_p - -end module const diff --git a/Project#03/fortran/src/hf.f90 b/Project#03/fortran/src/hf.f90 deleted file mode 100644 index 2525a96..0000000 --- a/Project#03/fortran/src/hf.f90 +++ /dev/null @@ -1,57 +0,0 @@ -module hf - use const - - implicit none - - contains - subroutine do_hartree_fock(sys, int_store) - use error_handling - use system - use read_in_integrals - use linalg - - type(int_store_t), intent(in) :: int_store - type(system_t), intent(in) :: sys - - type(mat_t) :: ovlp - - call init_mat_t(sys, int_store%ovlp, ovlp) - - call orthogonalise(ovlp) - - print*, ovlp%W - end subroutine do_hartree_fock - - - subroutine orthogonalise(mat) - ! For a symmetric matrix A we produce - ! A = CLC^(-1) - ! With L and C stored in a mat_t data structure - - use linalg - use error_handling - - type(mat_t), intent(inout) :: mat - - integer :: ierr - - call eigs(mat, ierr) - if (ierr /= 0) call error('hf::orthogonalise', 'Orthogonalisation failed!') - end subroutine orthogonalise - - subroutine init_mat_t(sys, matrix, mat) - use read_in_integrals - use linalg - use system - - type(system_t), intent(in) :: sys - real(p), intent(in) :: matrix(:,:) - type(mat_t), intent(out) :: mat - - mat%N = sys%nbasis - allocate(mat%A(mat%N, mat%N)) - mat%A(:,:) = matrix(:,:) - allocate(mat%W(sys%nbasis)) - end subroutine init_mat_t - -end module hf diff --git a/Project#03/fortran/t.dat b/Project#03/fortran/t.dat deleted file mode 100644 index 328ae64..0000000 --- a/Project#03/fortran/t.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 15.891123645988891 - 2 1 -0.085889884750479 - 2 2 0.472249956863652 - 3 1 -0.000000000000000 - 3 2 0.000000000000000 - 3 3 1.477728140458955 - 4 1 0.000000000000000 - 4 2 0.000000000000000 - 4 3 0.000000000000000 - 4 4 1.477728140458955 - 5 1 -0.000000000000000 - 5 2 -0.000000000000000 - 5 3 0.000000000000000 - 5 4 0.000000000000000 - 5 5 1.477728140458955 - 6 1 -0.010344430032030 - 6 2 0.108500715331350 - 6 3 0.152571116134591 - 6 4 -0.152571116134591 - 6 5 -0.152571116134591 - 6 6 0.760031756150991 - 7 1 -0.010344430032030 - 7 2 0.108500715331350 - 7 3 0.152571116134591 - 7 4 0.152571116134591 - 7 5 0.152571116134591 - 7 6 -0.005308006385401 - 7 7 0.760031756150991 - 8 1 -0.010344430032030 - 8 2 0.108500715331350 - 8 3 -0.152571116134591 - 8 4 0.152571116134591 - 8 5 -0.152571116134591 - 8 6 -0.005308006385401 - 8 7 -0.005308006385401 - 8 8 0.760031756150991 - 9 1 -0.010344430032030 - 9 2 0.108500715331350 - 9 3 -0.152571116134591 - 9 4 -0.152571116134591 - 9 5 0.152571116134590 - 9 6 -0.005308006385401 - 9 7 -0.005308006385401 - 9 8 -0.005308006385401 - 9 9 0.760031756150991 diff --git a/Project#03/fortran/v.dat b/Project#03/fortran/v.dat deleted file mode 100644 index 76b367c..0000000 --- a/Project#03/fortran/v.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 -35.603626980402581 - 2 1 -4.676755261049649 - 2 2 -7.084529072583363 - 3 1 0.000000000000000 - 3 2 -0.000000000000000 - 3 3 -7.042708592061365 - 4 1 -0.000000000000000 - 4 2 0.000000000000000 - 4 3 -0.000000000000000 - 4 4 -7.042708592061365 - 5 1 0.000000000000000 - 5 2 0.000000000000000 - 5 3 -0.000000000000000 - 5 4 0.000000000000000 - 5 5 -7.042708592061365 - 6 1 -1.207710997119606 - 6 2 -2.981540218150075 - 6 3 -1.511693653842257 - 6 4 1.511693653842256 - 6 5 1.511693653842257 - 6 6 -4.983518228353068 - 7 1 -1.207710997119606 - 7 2 -2.981540218150075 - 7 3 -1.511693653842256 - 7 4 -1.511693653842256 - 7 5 -1.511693653842256 - 7 6 -0.934142211713616 - 7 7 -4.983518228353068 - 8 1 -1.207710997119606 - 8 2 -2.981540218150075 - 8 3 1.511693653842256 - 8 4 -1.511693653842257 - 8 5 1.511693653842257 - 8 6 -0.934142211713617 - 8 7 -0.934142211713616 - 8 8 -4.983518228353068 - 9 1 -1.207710997119606 - 9 2 -2.981540218150075 - 9 3 1.511693653842257 - 9 4 1.511693653842257 - 9 5 -1.511693653842255 - 9 6 -0.934142211713616 - 9 7 -0.934142211713615 - 9 8 -0.934142211713616 - 9 9 -4.983518228353067 diff --git a/Project#03/hints/hint10-1.md b/Project#03/hints/hint10-1.md deleted file mode 100644 index 422bdcf..0000000 --- a/Project#03/hints/hint10-1.md +++ /dev/null @@ -1,40 +0,0 @@ -The iteration-by-iteration electronic and total energies for the H2O test case are as follows: - -``` - Iter E(elec) E(tot) Delta(E) RMS(D) - 00 -125.842077437699 -117.839710375888 - 01 -78.286583284740 -70.284216222929 47.555494152959 1.826673084479 - 02 -84.048316253435 -76.045949191625 -5.761732968696 0.479570364860 - 03 -82.716965960855 -74.714598899044 1.331350292581 0.086831688906 - 04 -82.987140757002 -74.984773695191 -0.270174796147 0.031026136359 - 05 -82.938133187513 -74.935766125703 0.049007569488 0.010799283179 - 06 -82.946271078699 -74.943904016889 -0.008137891186 0.005254826831 - 07 -82.944486784914 -74.942119723104 0.001784293785 0.002438579642 - 08 -82.944617252243 -74.942250190433 -0.000130467329 0.001177279531 - 09 -82.944503500703 -74.942136438892 0.000113751541 0.000564543180 - 10 -82.944478930626 -74.942111868815 0.000024570077 0.000272204992 - 11 -82.944461627684 -74.942094565874 0.000017302941 0.000131180309 - 12 -82.944454198375 -74.942087136564 0.000007429310 0.000063275666 - 13 -82.944450445051 -74.942083383241 0.000003753324 0.000030522547 - 14 -82.944448661686 -74.942081599875 0.000001783365 0.000014725847 - 15 -82.944447795931 -74.942080734120 0.000000865755 0.000007104836 - 16 -82.944447379016 -74.942080317206 0.000000416914 0.000003428026 - 17 -82.944447177685 -74.942080115875 0.000000201331 0.000001654014 - 18 -82.944447080565 -74.942080018755 0.000000097120 0.000000798065 - 19 -82.944447033699 -74.942079971888 0.000000046867 0.000000385069 - 20 -82.944447011086 -74.942079949276 0.000000022613 0.000000185798 - 21 -82.944447000175 -74.942079938365 0.000000010911 0.000000089648 - 22 -82.944446994911 -74.942079933100 0.000000005264 0.000000043256 - 23 -82.944446992371 -74.942079930560 0.000000002540 0.000000020871 - 24 -82.944446991145 -74.942079929334 0.000000001226 0.000000010070 - 25 -82.944446990554 -74.942079928743 0.000000000591 0.000000004859 - 26 -82.944446990268 -74.942079928458 0.000000000285 0.000000002345 - 27 -82.944446990130 -74.942079928320 0.000000000138 0.000000001131 - 28 -82.944446990064 -74.942079928254 0.000000000066 0.000000000546 - 29 -82.944446990032 -74.942079928222 0.000000000032 0.000000000263 - 30 -82.944446990016 -74.942079928206 0.000000000016 0.000000000127 - 31 -82.944446990009 -74.942079928199 0.000000000007 0.000000000061 - 32 -82.944446990005 -74.942079928195 0.000000000004 0.000000000030 - 33 -82.944446990004 -74.942079928193 0.000000000002 0.000000000014 - 34 -82.944446990003 -74.942079928192 0.000000000001 0.000000000007 -``` diff --git a/Project#03/hints/hint2-1.md b/Project#03/hints/hint2-1.md deleted file mode 100644 index b5217e6..0000000 --- a/Project#03/hints/hint2-1.md +++ /dev/null @@ -1,12 +0,0 @@ -The core Hamiltonian for the H2O test case is: -``` - 1 2 3 4 5 6 7 - - 1 -32.5773954 -7.5788328 0.0000000 -0.0144738 0.0000000 -1.2401023 -1.2401023 - 2 -7.5788328 -9.2009433 0.0000000 -0.1768902 0.0000000 -2.9067098 -2.9067098 - 3 0.0000000 0.0000000 -7.4588193 0.0000000 0.0000000 -1.6751501 1.6751501 - 4 -0.0144738 -0.1768902 0.0000000 -7.4153118 0.0000000 -1.3568683 -1.3568683 - 5 0.0000000 0.0000000 0.0000000 0.0000000 -7.3471449 0.0000000 0.0000000 - 6 -1.2401023 -2.9067098 -1.6751501 -1.3568683 0.0000000 -4.5401711 -1.0711459 - 7 -1.2401023 -2.9067098 1.6751501 -1.3568683 0.0000000 -1.0711459 -4.5401711 -``` diff --git a/Project#03/hints/hint3-1.md b/Project#03/hints/hint3-1.md deleted file mode 100644 index 1446996..0000000 --- a/Project#03/hints/hint3-1.md +++ /dev/null @@ -1,35 +0,0 @@ -## Symettric Matrices -How do we conveniently store the elements of the four-dimensional two-electron integral array in a one-dimensional array? Consider the lower triangle of an *n x n* symmetric matrix: - - - -The total number of elements in the lower triangle is *M = n(n+1)/2*. We could store these in a one-dimensional array by ordering them from top-to-bottom, left-to-right: - - - -How do we translate row (*i*) and column (*j*) indices of the matrix to the position in the linear array (*ij*)? - - - -Here's a code block to calculate the compound index using a standard [if-then-else conditional](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Control-Statements): -```c++ - int i, j, ij; - ... - if(i>j) ij = i*(i+1)/2 + j; - else ij = j*(j+1)/2 + i; -``` -Here's an equivalent piece of code that requires fewer keystrokes: -```c++ - int i, j, ij; - ... - ij = i>j ? i*(i+1)/2 + j : j*(j+1)/2 + i; -``` - -## Four-Dimensional Arrays -The eight-fold permutational symmetry of the two-electron repulsion integrals can be viewed similarly. The Mulliken-notation integrals are symmetric to permutations of the bra indices or of the ket indices. Hence, we can view the integral list as a symmetric "super-matrix" of the form: - - - -Thus, just as for the two-dimensional case above, we only need to store the lower triangle of this matrix, and a one-dimensional array of length *M(M+1)/2* will do the trick. Given four AO indices, *i*, *j*, *k*, and *l* corresponding to the integral, (ij|kl), we can translate these into compound row (*ij*) and column (*kl*) indices using the expression above, as well as the final compound index: - - diff --git a/Project#03/hints/hint3-2.md b/Project#03/hints/hint3-2.md deleted file mode 100644 index 77b74c5..0000000 --- a/Project#03/hints/hint3-2.md +++ /dev/null @@ -1,20 +0,0 @@ -If you've written your program so that the two-electron integrals are stored in a one-dimensional array, you may have recognized that your program spends quite a bit of its time calculating compound indices. Is there a way to speed up this process? Sure! Pre-compute the indices instead. Look again at the structure of a symmetric matrix, with the elements of the lower triangle numbered top-to-bottom/left-to-right: - - - -We calculate these above values from the raw row and column indices, *i* and *j*, respectively using: - - - -The expensive part of the above expression is the repeated evaluation of the *i(i+1)/2* and *j(j+1)/2* parts (which correspond to the first column of numbers in the above matrix). However, if we were to build an integer array (named `ioff`, for example) to store these values, then we could simplify the task to use array look-ups instead: -```c++ -ij = (i>j) ? ioff[i] + j : ioff[j] + i; -``` - -We can build the ioff array using a recursion: -```c++ -ioff[0] = 0; -for(int i=1; i < BIGNUM; i++) - ioff[i] = ioff[i-1] + i; -``` -where `BIGNUM` is some large number exceeding the maximum row/column dimension we expect to use in our calculations. diff --git a/Project#03/hints/hint3-3.md b/Project#03/hints/hint3-3.md deleted file mode 100644 index 87a6f2b..0000000 --- a/Project#03/hints/hint3-3.md +++ /dev/null @@ -1,43 +0,0 @@ -Previously the [Hessian](../../Project%2302/hints/hint1.md) ([Project #2](../../Project%2302/)) and the one-electron quantities so far in [Project 3](../../Project%2303) have been provided in an order that makes reading them in using a loop structure trivial. - -```c++ - ... - - FILE *input; - int a, b; - double **S; - - ... - - input = fopen("s.dat", "r"); - for(int i=0; i < nao; i++) { - for(int j=0; j <= i; j++) { - fscanf(hessian, "%d %d %lf", &a, &b, &S[i][j]); - S[j][i] = S[i][j]; - } - } - fclose(input); -``` - -However the two-electron integrals are not provided in this convenient ordering, you could go through the file and attempt to reorder them so that a loop structure works, or you could put the previously ignored index information you're reading with your fscanf to good use. This prevents the use of hard-wired loops that assume a specific ordering of the data, and it also prevents having to calculate how many elements are in the file to be read. - -```c++ - ... - - FILE *input; - int i, j, k, l; - double val; - double **TEI; - - ... - - input = fopen("eri.dat", "r"); - while(fscanf(input, "%d %d %d %d %lf", &i, &j, &k, &l, &val) != EOF) { - - ... - - TEI[ijkl] = val; - } - fclose(input); -``` -The `EOF` above is the [end-of-file](http://en.wikipedia.org/wiki/End-of-file) condition, so `!= EOF` means the above while loop scans the file until it reaches the end. diff --git a/Project#03/hints/hint4-1.md b/Project#03/hints/hint4-1.md deleted file mode 100644 index 73ae91c..0000000 --- a/Project#03/hints/hint4-1.md +++ /dev/null @@ -1,12 +0,0 @@ -The S-1/2 matrix for the H2O test case is: -``` - 1 2 3 4 5 6 7 - - 1 1.0236346 -0.1368547 -0.0000000 -0.0074873 -0.0000000 0.0190279 0.0190279 - 2 -0.1368547 1.1578632 0.0000000 0.0721601 0.0000000 -0.2223326 -0.2223326 - 3 -0.0000000 0.0000000 1.0733148 0.0000000 -0.0000000 -0.1757583 0.1757583 - 4 -0.0074873 0.0721601 0.0000000 1.0383050 0.0000000 -0.1184626 -0.1184626 - 5 -0.0000000 0.0000000 -0.0000000 0.0000000 1.0000000 -0.0000000 -0.0000000 - 6 0.0190279 -0.2223326 -0.1757583 -0.1184626 -0.0000000 1.1297234 -0.0625975 - 7 0.0190279 -0.2223326 0.1757583 -0.1184626 -0.0000000 -0.0625975 1.1297234 -``` diff --git a/Project#03/hints/hint5-1.md b/Project#03/hints/hint5-1.md deleted file mode 100644 index 7bd2dea..0000000 --- a/Project#03/hints/hint5-1.md +++ /dev/null @@ -1,13 +0,0 @@ -The initial Fock matrix in the orthogonal AO basis for the H2O test case is: - -``` - 1 2 3 4 5 6 7 - - 1 -32.2545866 -2.7914909 -0.0000000 0.0086110 0.0000000 -0.1812967 -0.1812967 - 2 -2.7914909 -8.2368891 -0.0000000 -0.2282926 0.0000000 -0.3857987 -0.3857987 - 3 -0.0000000 -0.0000000 -7.5428890 -0.0000000 0.0000000 -0.1132121 0.1132121 - 4 0.0086110 -0.2282926 -0.0000000 -7.4570295 -0.0000000 -0.1102196 -0.1102196 - 5 0.0000000 0.0000000 0.0000000 -0.0000000 -7.3471449 0.0000000 0.0000000 - 6 -0.1812967 -0.3857987 -0.1132121 -0.1102196 0.0000000 -4.0329547 -0.0446466 - 7 -0.1812967 -0.3857987 0.1132121 -0.1102196 0.0000000 -0.0446466 -4.0329547 -``` diff --git a/Project#03/hints/hint5-2.md b/Project#03/hints/hint5-2.md deleted file mode 100644 index e1be5eb..0000000 --- a/Project#03/hints/hint5-2.md +++ /dev/null @@ -1,13 +0,0 @@ -The initial MO coefficient matrix for the H2O test case is: - -``` - 1 2 3 4 5 6 7 - - 1 -1.0015436 0.2336245 0.0000000 0.0856842 0.0000000 -0.0482226 -0.0000000 - 2 0.0071893 -1.0579388 -0.0000000 -0.3601105 -0.0000000 0.4631213 0.0000000 - 3 -0.0000000 -0.0000000 1.0610702 0.0000000 -0.0000000 -0.0000000 0.2965071 - 4 0.0002671 -0.4272843 -0.0000000 0.9399425 0.0000000 0.2129401 0.0000000 - 5 0.0000000 0.0000000 -0.0000000 0.0000000 -1.0000000 -0.0000000 -0.0000000 - 6 -0.0018213 0.1492533 -0.1377210 -0.0378579 0.0000000 -0.7807003 -0.8501403 - 7 -0.0018213 0.1492533 0.1377210 -0.0378579 -0.0000000 -0.7807003 0.8501403 -``` diff --git a/Project#03/hints/hint5-3.md b/Project#03/hints/hint5-3.md deleted file mode 100644 index cdab244..0000000 --- a/Project#03/hints/hint5-3.md +++ /dev/null @@ -1,13 +0,0 @@ -The initial density matrix for the H2O test case is: - -``` - 1 2 3 4 5 6 7 - - 1 1.0650117 -0.2852166 -0.0000000 -0.0195534 -0.0000000 0.0334496 0.0334496 - 2 -0.2852166 1.2489657 0.0000000 0.1135594 0.0000000 -0.1442809 -0.1442809 - 3 -0.0000000 0.0000000 1.1258701 -0.0000000 -0.0000000 -0.1461317 0.1461317 - 4 -0.0195534 0.1135594 -0.0000000 1.0660638 0.0000000 -0.0993583 -0.0993583 - 5 -0.0000000 0.0000000 -0.0000000 0.0000000 1.0000000 -0.0000000 -0.0000000 - 6 0.0334496 -0.1442809 -0.1461317 -0.0993583 -0.0000000 0.0426802 0.0047460 - 7 0.0334496 -0.1442809 0.1461317 -0.0993583 -0.0000000 0.0047460 0.0426802 -``` diff --git a/Project#03/hints/hint6-1.md b/Project#03/hints/hint6-1.md deleted file mode 100644 index b0d9ebf..0000000 --- a/Project#03/hints/hint6-1.md +++ /dev/null @@ -1 +0,0 @@ -The initial Hartree-Fock electronic energy for the H2O test case is -125.842077437699 Hartrees. diff --git a/Project#03/hints/hint7-1.md b/Project#03/hints/hint7-1.md deleted file mode 100644 index e0e2226..0000000 --- a/Project#03/hints/hint7-1.md +++ /dev/null @@ -1,13 +0,0 @@ -The first-iteration Fock matrix in the AO basis for the H2O test case is: - -``` - 1 2 3 4 5 6 7 - - 1 -18.8132695 -4.8726875 -0.0000000 -0.0115290 0.0000000 -0.8067323 -0.8067323 - 2 -4.8726875 -1.7909029 -0.0000000 -0.1808692 0.0000000 -0.5790557 -0.5790557 - 3 -0.0000000 -0.0000000 0.1939644 0.0000000 0.0000000 -0.1708886 0.1708886 - 4 -0.0115290 -0.1808692 0.0000000 0.2391247 0.0000000 -0.1828683 -0.1828683 - 5 0.0000000 0.0000000 0.0000000 0.0000000 0.3091071 0.0000000 0.0000000 - 6 -0.8067323 -0.5790557 -0.1708886 -0.1828683 0.0000000 -0.1450338 -0.1846675 - 7 -0.8067323 -0.5790557 0.1708886 -0.1828683 0.0000000 -0.1846675 -0.1450338 -``` diff --git a/Project#03/hints/hint7-2.md b/Project#03/hints/hint7-2.md deleted file mode 100644 index 0e502aa..0000000 --- a/Project#03/hints/hint7-2.md +++ /dev/null @@ -1,22 +0,0 @@ -The following code illustrates the basic algorithm for building the Fock matrix (F) using the core Hamiltonian matrix (H), the density matrix (D), and the two-electron integrals stored in a one-dimensional array (TEI): -```c++ -for(int i=0; i < nao; i++) - for(int j=0; j < nao; j++) { - F[i][j] = H[i][j]; - for(int k=0; k < nao; k++) - for(int l=0; l < nao; l++) { - ij = INDEX(i,j); - kl = INDEX(k,l); - ijkl = INDEX(ij,kl); - ik = INDEX(i,k); - jl = INDEX(j,l); - ikjl = INDEX(ik,jl); - - F[i][j] += D[k][l] * (2.0 * TEI[ijkl] - TEI[ikjl]); - } - } -``` -The `INDEX` function is most easily defined as a macro using the `ioff` array explained in [an earlier hint](./hint3-2.md), e.g.: -```c++ -#define INDEX(i,j) (i>j) ? (ioff[i]+j) : (ioff[j]+i) -``` diff --git a/Project#03/input/ch4/STO-3G/enuc.dat b/Project#03/input/ch4/STO-3G/enuc.dat deleted file mode 100644 index feb8199..0000000 --- a/Project#03/input/ch4/STO-3G/enuc.dat +++ /dev/null @@ -1 +0,0 @@ - 13.497304462036480 diff --git a/Project#03/input/ch4/STO-3G/eri.dat b/Project#03/input/ch4/STO-3G/eri.dat deleted file mode 100644 index b1c1a16..0000000 --- a/Project#03/input/ch4/STO-3G/eri.dat +++ /dev/null @@ -1,912 +0,0 @@ - 1 1 1 1 3.541948297688456 - 2 1 1 1 0.576921328341946 - 2 2 1 1 0.854681772892244 - 2 1 2 1 0.111888125975301 - 2 2 2 1 0.205283870818581 - 2 2 2 2 0.624708798510611 - 3 3 1 1 0.852436095451127 - 4 4 1 1 0.852436095451127 - 5 5 1 1 0.852436095451127 - 3 1 3 1 0.020296465970775 - 4 1 4 1 0.020296465970775 - 5 1 5 1 0.020296465970775 - 3 3 2 1 0.205335088917950 - 4 4 2 1 0.205335088917950 - 5 5 2 1 0.205335088917950 - 3 2 3 1 0.030857749607787 - 4 2 4 1 0.030857749607787 - 5 2 5 1 0.030857749607787 - 3 3 2 2 0.624568373997849 - 4 4 2 2 0.624568373997849 - 5 5 2 2 0.624568373997849 - 3 2 3 2 0.137996275062609 - 4 2 4 2 0.137996275062609 - 5 2 5 2 0.137996275062609 - 3 3 3 3 0.672832726154768 - 4 3 4 3 0.036268641177034 - 4 4 3 3 0.600295443800700 - 4 4 4 4 0.672832726154768 - 5 3 5 3 0.036268641177034 - 5 4 5 4 0.036268641177034 - 5 5 3 3 0.600295443800700 - 5 5 4 4 0.600295443800700 - 5 5 5 5 0.672832726154768 - 6 1 1 1 0.147608605517858 - 6 2 1 1 0.335162193482858 - 6 1 2 1 0.028436223207717 - 6 2 2 1 0.081484132039537 - 6 1 2 2 0.052013862829475 - 6 2 2 2 0.270610027447356 - 6 3 1 1 0.160685542140597 - 6 4 1 1 -0.160685542140597 - 6 5 1 1 -0.160685542140597 - 6 1 3 1 0.001011537963698 - 6 1 4 1 -0.001011537963698 - 6 1 5 1 -0.001011537963698 - 6 3 2 1 0.039589644041248 - 6 4 2 1 -0.039589644041248 - 6 5 2 1 -0.039589644041248 - 6 2 3 1 0.004477861111553 - 6 2 4 1 -0.004477861111553 - 6 2 5 1 -0.004477861111553 - 6 1 3 2 0.001871693426017 - 6 1 4 2 -0.001871693426017 - 6 1 5 2 -0.001871693426017 - 6 3 2 2 0.139421122563721 - 6 4 2 2 -0.139421122563721 - 6 5 2 2 -0.139421122563721 - 6 2 3 2 0.030106293109745 - 6 2 4 2 -0.030106293109745 - 6 2 5 2 -0.030106293109745 - 6 3 3 1 0.010426154716997 - 6 3 4 1 -0.001906745560306 - 6 3 5 1 -0.001906745560306 - 6 4 3 1 -0.001906745560306 - 6 4 4 1 0.010426154716997 - 6 4 5 1 0.001906745560306 - 6 5 3 1 -0.001906745560306 - 6 5 4 1 0.001906745560306 - 6 5 5 1 0.010426154716997 - 6 1 3 3 0.052019626481534 - 6 1 4 3 -0.000184216227311 - 6 1 4 4 0.052019626481534 - 6 1 5 3 -0.000184216227311 - 6 1 5 4 0.000184216227311 - 6 1 5 5 0.052019626481534 - 6 3 3 2 0.058661644705102 - 6 3 4 2 -0.014479739998984 - 6 3 5 2 -0.014479739998984 - 6 4 3 2 -0.014479739998984 - 6 4 4 2 0.058661644705102 - 6 4 5 2 0.014479739998984 - 6 5 3 2 -0.014479739998984 - 6 5 4 2 0.014479739998984 - 6 5 5 2 0.058661644705102 - 6 2 3 3 0.270528257787828 - 6 2 4 3 -0.006219383581894 - 6 2 4 4 0.270528257787828 - 6 2 5 3 -0.006219383581894 - 6 2 5 4 0.006219383581894 - 6 2 5 5 0.270528257787828 - 6 3 3 3 0.147350449688697 - 6 3 4 3 -0.009008061860584 - 6 3 4 4 0.135383283308776 - 6 3 5 3 -0.009008061860584 - 6 3 5 4 0.003024478670624 - 6 3 5 5 0.135383283308776 - 6 4 3 3 -0.135383283308776 - 6 4 4 3 0.009008061860584 - 6 4 4 4 -0.147350449688697 - 6 4 5 3 0.003024478670624 - 6 4 5 4 -0.009008061860584 - 6 4 5 5 -0.135383283308776 - 6 5 3 3 -0.135383283308776 - 6 5 4 3 0.003024478670624 - 6 5 4 4 -0.135383283308776 - 6 5 5 3 0.009008061860584 - 6 5 5 4 -0.009008061860584 - 6 5 5 5 -0.147350449688697 - 6 6 1 1 0.476243219694492 - 6 1 6 1 0.007392439568588 - 6 6 2 1 0.117779163679254 - 6 2 6 1 0.021572281521988 - 6 6 2 2 0.442741256057859 - 6 2 6 2 0.150398371320733 - 6 6 3 1 0.008468426244723 - 6 6 4 1 -0.008468426244723 - 6 6 5 1 -0.008468426244723 - 6 3 6 1 0.011004027466676 - 6 4 6 1 -0.011004027466676 - 6 5 6 1 -0.011004027466676 - 6 6 3 2 0.075171682582069 - 6 6 4 2 -0.075171682582069 - 6 6 5 2 -0.075171682582069 - 6 3 6 2 0.092137140323668 - 6 4 6 2 -0.092137140323668 - 6 5 6 2 -0.092137140323668 - 6 6 3 3 0.442576919468473 - 6 6 4 3 -0.023480017154601 - 6 6 4 4 0.442576919468473 - 6 6 5 3 -0.023480017154601 - 6 6 5 4 0.023480017154601 - 6 6 5 5 0.442576919468473 - 6 3 6 3 0.074541738631701 - 6 4 6 3 -0.055427849495928 - 6 4 6 4 0.074541738631701 - 6 5 6 3 -0.055427849495928 - 6 5 6 4 0.055427849495928 - 6 5 6 5 0.074541738631701 - 6 6 6 1 0.031703797879678 - 6 6 6 2 0.304981529941436 - 6 6 6 3 0.206879432071914 - 6 6 6 4 -0.206879432071914 - 6 6 6 5 -0.206879432071914 - 6 6 6 6 0.774605895725855 - 7 1 1 1 0.147608605517858 - 7 2 1 1 0.335162193482858 - 7 1 2 1 0.028436223207717 - 7 2 2 1 0.081484132039537 - 7 1 2 2 0.052013862829475 - 7 2 2 2 0.270610027447356 - 7 3 1 1 0.160685542140597 - 7 4 1 1 0.160685542140597 - 7 5 1 1 0.160685542140597 - 7 1 3 1 0.001011537963698 - 7 1 4 1 0.001011537963698 - 7 1 5 1 0.001011537963698 - 7 3 2 1 0.039589644041248 - 7 4 2 1 0.039589644041248 - 7 5 2 1 0.039589644041248 - 7 2 3 1 0.004477861111553 - 7 2 4 1 0.004477861111553 - 7 2 5 1 0.004477861111553 - 7 1 3 2 0.001871693426017 - 7 1 4 2 0.001871693426017 - 7 1 5 2 0.001871693426017 - 7 3 2 2 0.139421122563721 - 7 4 2 2 0.139421122563721 - 7 5 2 2 0.139421122563721 - 7 2 3 2 0.030106293109745 - 7 2 4 2 0.030106293109745 - 7 2 5 2 0.030106293109745 - 7 3 3 1 0.010426154716997 - 7 3 4 1 0.001906745560306 - 7 3 5 1 0.001906745560306 - 7 4 3 1 0.001906745560306 - 7 4 4 1 0.010426154716997 - 7 4 5 1 0.001906745560306 - 7 5 3 1 0.001906745560306 - 7 5 4 1 0.001906745560306 - 7 5 5 1 0.010426154716997 - 7 1 3 3 0.052019626481534 - 7 1 4 3 0.000184216227311 - 7 1 4 4 0.052019626481534 - 7 1 5 3 0.000184216227311 - 7 1 5 4 0.000184216227311 - 7 1 5 5 0.052019626481534 - 7 3 3 2 0.058661644705102 - 7 3 4 2 0.014479739998984 - 7 3 5 2 0.014479739998984 - 7 4 3 2 0.014479739998984 - 7 4 4 2 0.058661644705102 - 7 4 5 2 0.014479739998984 - 7 5 3 2 0.014479739998984 - 7 5 4 2 0.014479739998984 - 7 5 5 2 0.058661644705102 - 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a/Project#03/input/ch4/STO-3G/input.dat b/Project#03/input/ch4/STO-3G/input.dat deleted file mode 100644 index 6dfb483..0000000 --- a/Project#03/input/ch4/STO-3G/input.dat +++ /dev/null @@ -1,43 +0,0 @@ -psi: ( - label = "CH4 SCF Test Case" - wfn = scf - jobtype = oeprop - reference = rhf - basis = "STO-3G" - units = angstrom - subgroup = c1 - delete_tei = false - delete_oei = false - zmat = ( - C - H 1 r - H 1 r 2 td - H 1 r 2 td 3 d - H 1 r 2 td 4 d - ) - zvars = ( - r 1.085 - td 109.47122063449069136958 - d 120.0 - ) -) - -basis: ( - carbon: "STO-3G" = - ( (S ( 71.61683730 0.15432900) - ( 13.04509630 0.53532810) - ( 3.53051220 0.44463450) ) - (S ( 2.94124940 -0.09996720) - ( 0.68348310 0.39951280) - ( 0.22228990 0.70011550) ) - (P ( 2.94124940 0.15591630) - ( 0.68348310 0.60768370) - ( 0.22228990 0.39195740) ) - ) - - hydrogen: "STO-3G"= - ( (S ( 3.42525090 0.15432890) - ( 0.62391370 0.53532810) - ( 0.16885540 0.44463450) ) - ) -) diff --git a/Project#03/input/ch4/STO-3G/mux.dat b/Project#03/input/ch4/STO-3G/mux.dat deleted file mode 100644 index 9dca8dd..0000000 --- a/Project#03/input/ch4/STO-3G/mux.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 0.000000000000000 - 2 1 0.000000000000000 - 2 2 0.000000000000000 - 3 1 -0.071855488532817 - 3 2 -0.838743574800986 - 3 3 0.000000000000000 - 4 1 -0.000000000000000 - 4 2 0.000000000000000 - 4 3 -0.000000000000000 - 4 4 0.000000000000000 - 5 1 0.000000000000000 - 5 2 0.000000000000000 - 5 3 -0.000000000000000 - 5 4 0.000000000000000 - 5 5 0.000000000000000 - 6 1 -0.004780775261548 - 6 2 -0.306592476518555 - 6 3 -0.519567036508228 - 6 4 0.163831354490276 - 6 5 0.163831354490276 - 6 6 -1.183771681897730 - 7 1 -0.004780775261548 - 7 2 -0.306592476518555 - 7 3 -0.519567036508228 - 7 4 -0.163831354490276 - 7 5 -0.163831354490276 - 7 6 -0.202918556316052 - 7 7 -1.183771681897730 - 8 1 0.004780775261548 - 8 2 0.306592476518555 - 8 3 -0.519567036508228 - 8 4 0.163831354490276 - 8 5 -0.163831354490276 - 8 6 -0.000000000000000 - 8 7 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diff --git a/Project#03/input/h2o/DZ/input.dat b/Project#03/input/h2o/DZ/input.dat deleted file mode 100644 index c9eeb62..0000000 --- a/Project#03/input/h2o/DZ/input.dat +++ /dev/null @@ -1,12 +0,0 @@ -psi: ( - label = "H2O SCF Test Case" - memory = (10.0 MB) - wfn = scf - jobtype = oeprop - delete_tei = false - delete_oei = false - reference = rhf - basis = "DZ" - subgroup = c1 - zmat = ((o) (h 1 1.1) (h 1 1.1 2 104.0)) -) diff --git a/Project#03/input/h2o/DZ/mux.dat b/Project#03/input/h2o/DZ/mux.dat deleted file mode 100644 index 900a852..0000000 --- a/Project#03/input/h2o/DZ/mux.dat +++ /dev/null @@ -1,105 +0,0 @@ - 1 1 -0.000000000000000 - 2 1 -0.000000000000000 - 2 2 -0.000000000000000 - 3 1 -0.000000000000000 - 3 2 -0.000000000000000 - 3 3 -0.000000000000000 - 4 1 -0.000000000000000 - 4 2 -0.000000000000000 - 4 3 -0.000000000000000 - 4 4 -0.000000000000000 - 5 1 -0.065756994029223 - 5 2 -0.076390812514647 - 5 3 -0.495548317796719 - 5 4 -0.578524588047388 - 5 5 -0.000000000000000 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-0.000000000000000 - 26 19 0.000000000000000 - 26 20 0.000000000000000 - 26 21 -0.109166181788804 - 26 22 -0.000000000000000 - 26 23 -0.000000000000000 - 26 24 -0.000000000000000 - 26 25 0.000000000000000 - 26 26 -4.768931533722705 diff --git a/Project#03/input/h2o/STO-3G/enuc.dat b/Project#03/input/h2o/STO-3G/enuc.dat deleted file mode 100644 index 6b08fe4..0000000 --- a/Project#03/input/h2o/STO-3G/enuc.dat +++ /dev/null @@ -1 +0,0 @@ - 8.002367061810450 diff --git a/Project#03/input/h2o/STO-3G/geom.dat b/Project#03/input/h2o/STO-3G/geom.dat deleted file mode 100644 index 99b165d..0000000 --- a/Project#03/input/h2o/STO-3G/geom.dat +++ /dev/null @@ -1,4 +0,0 @@ -3 -8.000000000000 0.000000000000 -0.143225816552 0.000000000000 -1.000000000000 1.638036840407 1.136548822547 -0.000000000000 -1.000000000000 -1.638036840407 1.136548822547 -0.000000000000 diff --git a/Project#03/output/ch4/STO-3G/output.txt b/Project#03/output/ch4/STO-3G/output.txt deleted file mode 100644 index 933d4ef..0000000 --- a/Project#03/output/ch4/STO-3G/output.txt +++ /dev/null @@ -1,187 +0,0 @@ - -Nuclear repulsion energy = 13.4973044620 - - Overlap Integrals: - - 1 2 3 4 5 6 7 8 9 - - 1 1.0000000 0.2483624 0.0000000 -0.0000000 0.0000000 0.0630068 0.0630068 0.0630068 0.0630068 - 2 0.2483624 1.0000000 0.0000000 0.0000000 0.0000000 0.4936348 0.4936348 0.4936348 0.4936348 - 3 0.0000000 0.0000000 1.0000000 0.0000000 0.0000000 0.2707690 0.2707690 -0.2707690 -0.2707690 - 4 -0.0000000 0.0000000 0.0000000 1.0000000 0.0000000 -0.2707690 0.2707690 0.2707690 -0.2707690 - 5 0.0000000 0.0000000 0.0000000 0.0000000 1.0000000 -0.2707690 0.2707690 -0.2707690 0.2707690 - 6 0.0630068 0.4936348 0.2707690 -0.2707690 -0.2707690 1.0000000 0.1714170 0.1714170 0.1714170 - 7 0.0630068 0.4936348 0.2707690 0.2707690 0.2707690 0.1714170 1.0000000 0.1714170 0.1714170 - 8 0.0630068 0.4936348 -0.2707690 0.2707690 -0.2707690 0.1714170 0.1714170 1.0000000 0.1714170 - 9 0.0630068 0.4936348 -0.2707690 -0.2707690 0.2707690 0.1714170 0.1714170 0.1714170 1.0000000 - - Kinetic-Energy Integrals: - - 1 2 3 4 5 6 7 8 9 - - 1 15.8911236 -0.0858899 -0.0000000 0.0000000 -0.0000000 -0.0103444 -0.0103444 -0.0103444 -0.0103444 - 2 -0.0858899 0.4722500 0.0000000 0.0000000 -0.0000000 0.1085007 0.1085007 0.1085007 0.1085007 - 3 -0.0000000 0.0000000 1.4777281 0.0000000 0.0000000 0.1525711 0.1525711 -0.1525711 -0.1525711 - 4 0.0000000 0.0000000 0.0000000 1.4777281 0.0000000 -0.1525711 0.1525711 0.1525711 -0.1525711 - 5 -0.0000000 -0.0000000 0.0000000 0.0000000 1.4777281 -0.1525711 0.1525711 -0.1525711 0.1525711 - 6 -0.0103444 0.1085007 0.1525711 -0.1525711 -0.1525711 0.7600318 -0.0053080 -0.0053080 -0.0053080 - 7 -0.0103444 0.1085007 0.1525711 0.1525711 0.1525711 -0.0053080 0.7600318 -0.0053080 -0.0053080 - 8 -0.0103444 0.1085007 -0.1525711 0.1525711 -0.1525711 -0.0053080 -0.0053080 0.7600318 -0.0053080 - 9 -0.0103444 0.1085007 -0.1525711 -0.1525711 0.1525711 -0.0053080 -0.0053080 -0.0053080 0.7600318 - - Nuclear Attraction Integrals: - - 1 2 3 4 5 6 7 8 9 - - 1 -35.6036270 -4.6767553 0.0000000 -0.0000000 0.0000000 -1.2077110 -1.2077110 -1.2077110 -1.2077110 - 2 -4.6767553 -7.0845291 -0.0000000 0.0000000 0.0000000 -2.9815402 -2.9815402 -2.9815402 -2.9815402 - 3 0.0000000 -0.0000000 -7.0427086 -0.0000000 -0.0000000 -1.5116937 -1.5116937 1.5116937 1.5116937 - 4 -0.0000000 0.0000000 -0.0000000 -7.0427086 0.0000000 1.5116937 -1.5116937 -1.5116937 1.5116937 - 5 0.0000000 0.0000000 -0.0000000 0.0000000 -7.0427086 1.5116937 -1.5116937 1.5116937 -1.5116937 - 6 -1.2077110 -2.9815402 -1.5116937 1.5116937 1.5116937 -4.9835182 -0.9341422 -0.9341422 -0.9341422 - 7 -1.2077110 -2.9815402 -1.5116937 -1.5116937 -1.5116937 -0.9341422 -4.9835182 -0.9341422 -0.9341422 - 8 -1.2077110 -2.9815402 1.5116937 -1.5116937 1.5116937 -0.9341422 -0.9341422 -4.9835182 -0.9341422 - 9 -1.2077110 -2.9815402 1.5116937 1.5116937 -1.5116937 -0.9341422 -0.9341422 -0.9341422 -4.9835182 - - Core Hamiltonian: - - 1 2 3 4 5 6 7 8 9 - - 1 -19.7125033 -4.7626451 0.0000000 0.0000000 0.0000000 -1.2180554 -1.2180554 -1.2180554 -1.2180554 - 2 -4.7626451 -6.6122791 0.0000000 0.0000000 0.0000000 -2.8730395 -2.8730395 -2.8730395 -2.8730395 - 3 0.0000000 0.0000000 -5.5649805 0.0000000 0.0000000 -1.3591225 -1.3591225 1.3591225 1.3591225 - 4 0.0000000 0.0000000 0.0000000 -5.5649805 0.0000000 1.3591225 -1.3591225 -1.3591225 1.3591225 - 5 0.0000000 0.0000000 0.0000000 0.0000000 -5.5649805 1.3591225 -1.3591225 1.3591225 -1.3591225 - 6 -1.2180554 -2.8730395 -1.3591225 1.3591225 1.3591225 -4.2234865 -0.9394502 -0.9394502 -0.9394502 - 7 -1.2180554 -2.8730395 -1.3591225 -1.3591225 -1.3591225 -0.9394502 -4.2234865 -0.9394502 -0.9394502 - 8 -1.2180554 -2.8730395 1.3591225 -1.3591225 1.3591225 -0.9394502 -0.9394502 -4.2234865 -0.9394502 - 9 -1.2180554 -2.8730395 1.3591225 1.3591225 -1.3591225 -0.9394502 -0.9394502 -0.9394502 -4.2234865 - - S^-1/2 Matrix: - - 1 2 3 4 5 6 7 8 9 - - 1 1.0299976 -0.1813138 0.0000000 0.0000000 0.0000000 0.0261560 0.0261560 0.0261560 0.0261560 - 2 -0.1813138 1.5904476 0.0000000 0.0000000 -0.0000000 -0.3473780 -0.3473780 -0.3473780 -0.3473780 - 3 0.0000000 0.0000000 1.1753346 -0.0000000 0.0000000 -0.2039715 -0.2039715 0.2039715 0.2039715 - 4 0.0000000 0.0000000 -0.0000000 1.1753346 0.0000000 0.2039715 -0.2039715 -0.2039715 0.2039715 - 5 0.0000000 -0.0000000 0.0000000 0.0000000 1.1753346 0.2039715 -0.2039715 0.2039715 -0.2039715 - 6 0.0261560 -0.3473780 -0.2039715 0.2039715 0.2039715 1.2764126 -0.0280511 -0.0280511 -0.0280511 - 7 0.0261560 -0.3473780 -0.2039715 -0.2039715 -0.2039715 -0.0280511 1.2764126 -0.0280511 -0.0280511 - 8 0.0261560 -0.3473780 0.2039715 -0.2039715 0.2039715 -0.0280511 -0.0280511 1.2764126 -0.0280511 - 9 0.0261560 -0.3473780 0.2039715 0.2039715 -0.2039715 -0.0280511 -0.0280511 -0.0280511 1.2764126 - - Initial F' Matrix: - - 1 2 3 4 5 6 7 8 9 - - 1 -19.5241878 -1.5499726 -0.0000000 -0.0000000 -0.0000000 -0.2141242 -0.2141242 -0.2141242 -0.2141242 - 2 -1.5499726 -5.9413680 -0.0000000 -0.0000000 -0.0000000 -0.3620641 -0.3620641 -0.3620641 -0.3620641 - 3 -0.0000000 -0.0000000 -5.6274166 0.0000000 -0.0000000 -0.1020488 -0.1020488 0.1020488 0.1020488 - 4 -0.0000000 -0.0000000 0.0000000 -5.6274166 -0.0000000 0.1020488 -0.1020488 -0.1020488 0.1020488 - 5 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -5.6274166 0.1020488 -0.1020488 0.1020488 -0.1020488 - 6 -0.2141242 -0.3620641 -0.1020488 0.1020488 0.1020488 -3.6394349 -0.0181358 -0.0181358 -0.0181358 - 7 -0.2141242 -0.3620641 -0.1020488 -0.1020488 -0.1020488 -0.0181358 -3.6394349 -0.0181358 -0.0181358 - 8 -0.2141242 -0.3620641 0.1020488 -0.1020488 0.1020488 -0.0181358 -0.0181358 -3.6394349 -0.0181358 - 9 -0.2141242 -0.3620641 0.1020488 0.1020488 -0.1020488 -0.0181358 -0.0181358 -0.0181358 -3.6394349 - - Initial C Matrix: - - 1 2 3 4 5 6 7 8 9 - - 1 -1.0039247 -0.2792065 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 -0.1033689 - 2 0.0216750 1.3402945 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 1.1172400 - 3 -0.0000000 -0.0000000 0.1247255 -0.9129721 0.6515652 0.4169482 0.0946867 0.3023337 0.0000000 - 4 -0.0000000 0.0000000 -0.8530198 0.3484706 0.6515652 -0.1264730 -0.4084311 0.3023337 -0.0000000 - 5 -0.0000000 -0.0000000 -0.7282943 -0.5645015 -0.6515652 0.2904752 -0.3137444 -0.3023337 0.0000000 - 6 -0.0054559 -0.1660333 -0.2080003 0.0849710 -0.0794388 -0.3233390 -1.0441886 -0.3864709 -0.6701712 - 7 -0.0054559 -0.1660333 0.1775872 0.1376480 -0.0794388 -0.7426244 0.8021140 -0.3864709 -0.6701712 - 8 -0.0054559 -0.1660333 0.0304131 -0.2226191 -0.0794388 1.0659633 0.2420745 -0.3864709 -0.6701712 - 9 -0.0054559 -0.1660333 0.0000000 -0.0000000 0.2383165 0.0000000 -0.0000000 1.1594126 -0.6701712 - - Initial Density Matrix: - - 1 2 3 4 5 6 7 8 9 - - 1 1.0858211 -0.3959790 0.0000000 -0.0000000 0.0000000 0.0518349 0.0518349 0.0518349 0.0518349 - 2 -0.3959790 1.7968591 0.0000000 0.0000000 -0.0000000 -0.2226517 -0.2226517 -0.2226517 -0.2226517 - 3 0.0000000 0.0000000 1.2736118 -0.0000000 0.0000000 -0.1552787 -0.1552787 0.1552787 0.1552787 - 4 -0.0000000 0.0000000 -0.0000000 1.2736118 -0.0000000 0.1552787 -0.1552787 -0.1552787 0.1552787 - 5 0.0000000 -0.0000000 0.0000000 -0.0000000 1.2736118 0.1552787 -0.1552787 0.1552787 -0.1552787 - 6 0.0518349 -0.2226517 -0.1552787 0.1552787 0.1552787 0.0843915 0.0086652 0.0086652 0.0086652 - 7 0.0518349 -0.2226517 -0.1552787 -0.1552787 -0.1552787 0.0086652 0.0843915 0.0086652 0.0086652 - 8 0.0518349 -0.2226517 0.1552787 -0.1552787 0.1552787 0.0086652 0.0086652 0.0843915 0.0086652 - 9 0.0518349 -0.2226517 0.1552787 0.1552787 -0.1552787 0.0086652 0.0086652 0.0086652 0.0843915 - - - Iter E(elec) E(tot) Delta(E) RMS(D) - 00 -85.245230708238 -71.747926246202 - - Fock Matrix: - - 1 2 3 4 5 6 7 8 9 - - 1 -8.9530154 -2.5417508 -0.0000000 -0.0000000 -0.0000000 -0.6617374 -0.6617374 -0.6617374 -0.6617374 - 2 -2.5417508 -0.8174464 -0.0000000 -0.0000000 0.0000000 -0.3883845 -0.3883845 -0.3883845 -0.3883845 - 3 -0.0000000 -0.0000000 0.4192075 0.0000000 0.0000000 -0.0541874 -0.0541874 0.0541874 0.0541874 - 4 -0.0000000 -0.0000000 0.0000000 0.4192075 -0.0000000 0.0541874 -0.0541874 -0.0541874 0.0541874 - 5 -0.0000000 0.0000000 0.0000000 -0.0000000 0.4192075 0.0541874 -0.0541874 0.0541874 -0.0541874 - 6 -0.6617374 -0.3883845 -0.0541874 0.0541874 0.0541874 0.0420011 -0.1549906 -0.1549906 -0.1549906 - 7 -0.6617374 -0.3883845 -0.0541874 -0.0541874 -0.0541874 -0.1549906 0.0420011 -0.1549906 -0.1549906 - 8 -0.6617374 -0.3883845 0.0541874 -0.0541874 0.0541874 -0.1549906 -0.1549906 0.0420011 -0.1549906 - 9 -0.6617374 -0.3883845 0.0541874 0.0541874 -0.0541874 -0.1549906 -0.1549906 -0.1549906 0.0420011 - 01 -47.644058278702 -34.146753816666 37.601172429536 3.218271155854 - 02 -54.267475123789 -40.770170661752 -6.623416845086 0.552284449568 - 03 -53.033759515927 -39.536455053891 1.233715607861 0.097563795703 - 04 -53.257610133322 -39.760305671285 -0.223850617394 0.017000394210 - 05 -53.218263252162 -39.720958790126 0.039346881159 0.003063617994 - 06 -53.225197726849 -39.727893264812 -0.006934474686 0.000533175256 - 07 -53.223971779086 -39.726667317050 0.001225947762 0.000098921759 - 08 -53.224187311711 -39.726882849675 -0.000215532625 0.000017335751 - 09 -53.224149109165 -39.726844647129 0.000038202546 0.000003438401 - 10 -53.224155802847 -39.726851340811 -0.000006693682 0.000000633546 - 11 -53.224154610801 -39.726850148764 0.000001192047 0.000000140618 - 12 -53.224154818281 -39.726850356245 -0.000000207481 0.000000028918 - 13 -53.224154780986 -39.726850318949 0.000000037295 0.000000007048 - 14 -53.224154787392 -39.726850325356 -0.000000006406 0.000000001602 - 15 -53.224154786219 -39.726850324183 0.000000001173 0.000000000403 - 16 -53.224154786415 -39.726850324379 -0.000000000196 0.000000000096 - 17 -53.224154786378 -39.726850324342 0.000000000037 0.000000000024 - 18 -53.224154786384 -39.726850324348 -0.000000000006 0.000000000006 - 19 -53.224154786383 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0.0000000 0.2029186 1.1837717 - - 1 2 3 4 5 6 7 8 9 - - 1 1.0329323 -0.1010877 -0.0000000 0.0000000 0.0000000 -0.0469085 -0.0469085 -0.0469085 -0.0469085 - 2 -0.1010877 0.3960228 0.0000000 -0.0000000 -0.0000000 0.1131900 0.1131900 0.1131900 0.1131900 - 3 -0.0000000 0.0000000 0.3268651 0.0000000 0.0000000 0.1721029 0.1721029 -0.1721029 -0.1721029 - 4 0.0000000 -0.0000000 0.0000000 0.3268651 -0.0000000 -0.1721029 0.1721029 0.1721029 -0.1721029 - 5 0.0000000 -0.0000000 0.0000000 -0.0000000 0.3268651 -0.1721029 0.1721029 -0.1721029 0.1721029 - 6 -0.0469085 0.1131900 0.1721029 -0.1721029 -0.1721029 0.3045239 -0.0579428 -0.0579428 -0.0579428 - 7 -0.0469085 0.1131900 0.1721029 0.1721029 0.1721029 -0.0579428 0.3045239 -0.0579428 -0.0579428 - 8 -0.0469085 0.1131900 -0.1721029 0.1721029 -0.1721029 -0.0579428 -0.0579428 0.3045239 -0.0579428 - 9 -0.0469085 0.1131900 -0.1721029 -0.1721029 0.1721029 -0.0579428 -0.0579428 -0.0579428 0.3045239 - -Mu-X = -0.000000000000 -Mu-Y = 0.000000000000 -Mu-Z = 0.000000000000 -Total dipole moment (au) = 0.000000000000 - -Charge on atom 0: -0.260430681332 -Charge on atom 1: 0.065107670333 -Charge on atom 2: 0.065107670333 -Charge on atom 3: 0.065107670333 -Charge on atom 4: 0.065107670333 diff --git a/Project#03/output/h2o/DZ/output.txt b/Project#03/output/h2o/DZ/output.txt deleted file mode 100644 index e1cd62c..0000000 --- a/Project#03/output/h2o/DZ/output.txt +++ /dev/null @@ -1,499 +0,0 @@ - -Nuclear repulsion energy = 8.0023670618 - - Overlap Integrals: - - 1 2 3 4 5 6 7 8 9 10 - - 1 1.0000000 0.8380557 0.3393514 0.1609665 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 2 0.8380557 1.0000000 0.4321873 0.1943843 -0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 3 0.3393514 0.4321873 1.0000000 0.7764487 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 4 0.1609665 0.1943843 0.7764487 1.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 5 0.0000000 -0.0000000 0.0000000 0.0000000 1.0000000 0.0000000 -0.0000000 0.5059985 0.0000000 0.0000000 - 6 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 1.0000000 0.0000000 0.0000000 0.5059985 0.0000000 - 7 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 1.0000000 0.0000000 0.0000000 0.5059985 - 8 0.0000000 0.0000000 0.0000000 0.0000000 0.5059985 0.0000000 0.0000000 1.0000000 0.0000000 0.0000000 - 9 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.5059985 0.0000000 0.0000000 1.0000000 0.0000000 - 10 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.5059985 0.0000000 0.0000000 1.0000000 - 11 0.0179951 0.0199736 0.1595600 0.3395977 0.2070784 0.1617873 -0.0000000 0.4236441 0.3309871 -0.0000000 - 12 0.0552886 0.0653163 0.3279305 0.5981919 0.1604978 0.1253946 -0.0000000 0.4491494 0.3509139 -0.0000000 - 13 0.0179951 0.0199736 0.1595600 0.3395977 -0.2070784 0.1617873 -0.0000000 -0.4236441 0.3309871 -0.0000000 - 14 0.0552886 0.0653163 0.3279305 0.5981919 -0.1604978 0.1253946 -0.0000000 -0.4491494 0.3509139 -0.0000000 - - 11 12 13 14 - - 1 0.0179951 0.0552886 0.0179951 0.0552886 - 2 0.0199736 0.0653163 0.0199736 0.0653163 - 3 0.1595600 0.3279305 0.1595600 0.3279305 - 4 0.3395977 0.5981919 0.3395977 0.5981919 - 5 0.2070784 0.1604978 -0.2070784 -0.1604978 - 6 0.1617873 0.1253946 0.1617873 0.1253946 - 7 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 8 0.4236441 0.4491494 -0.4236441 -0.4491494 - 9 0.3309871 0.3509139 0.3309871 0.3509139 - 10 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 11 1.0000000 0.6830602 0.0208962 0.1481732 - 12 0.6830602 1.0000000 0.1481732 0.3855594 - 13 0.0208962 0.1481732 1.0000000 0.6830602 - 14 0.1481732 0.3855594 0.6830602 1.0000000 - - Kinetic-Energy Integrals: - - 1 2 3 4 5 6 7 8 9 10 - - 1 52.6148950 15.6610148 0.8339502 0.1307410 -0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 - 2 15.6610148 14.2983000 1.1091549 0.1611538 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 - 3 0.8339502 1.1091549 1.4097000 0.5088398 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 4 0.1307410 0.1611538 0.5088398 0.4269000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 5 -0.0000000 -0.0000000 0.0000000 0.0000000 3.6349776 0.0000000 -0.0000000 0.4322940 0.0000000 -0.0000000 - 6 0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 3.6349776 0.0000000 0.0000000 0.4322940 0.0000000 - 7 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 3.6349776 -0.0000000 0.0000000 0.4322940 - 8 0.0000000 -0.0000000 0.0000000 0.0000000 0.4322940 0.0000000 -0.0000000 0.5342500 0.0000000 0.0000000 - 9 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.4322940 0.0000000 0.0000000 0.5342500 0.0000000 - 10 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.4322940 0.0000000 0.0000000 0.5342500 - 11 -0.0224048 -0.0283206 -0.0391207 0.0846346 0.1088756 0.0850630 -0.0000000 0.2498937 0.1952384 -0.0000000 - 12 0.0143865 0.0170052 0.0837195 0.1344271 0.0876121 0.0684501 -0.0000000 0.1813047 0.1416507 -0.0000000 - 13 -0.0224048 -0.0283206 -0.0391207 0.0846346 -0.1088756 0.0850630 -0.0000000 -0.2498937 0.1952384 -0.0000000 - 14 0.0143865 0.0170052 0.0837195 0.1344271 -0.0876121 0.0684501 -0.0000000 -0.1813047 0.1416507 -0.0000000 - - 11 12 13 14 - - 1 -0.0224048 0.0143865 -0.0224048 0.0143865 - 2 -0.0283206 0.0170052 -0.0283206 0.0170052 - 3 -0.0391207 0.0837195 -0.0391207 0.0837195 - 4 0.0846346 0.1344271 0.0846346 0.1344271 - 5 0.1088756 0.0876121 -0.1088756 -0.0876121 - 6 0.0850630 0.0684501 0.0850630 0.0684501 - 7 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 8 0.2498937 0.1813047 -0.2498937 -0.1813047 - 9 0.1952384 0.1416507 0.1952384 0.1416507 - 10 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 11 1.4157260 0.2925739 -0.0301548 -0.0012203 - 12 0.2925739 0.2664000 -0.0012203 0.0374519 - 13 -0.0301548 -0.0012203 1.4157260 0.2925739 - 14 -0.0012203 0.0374519 0.2925739 0.2664000 - - Nuclear Attraction Integrals: - - 1 2 3 4 5 6 7 8 9 10 - - 1 -82.4990426 -47.8119798 -12.5269876 -5.4491024 0.0000000 -0.0187383 0.0000000 0.0000000 -0.0030616 0.0000000 - 2 -47.8119798 -40.3766945 -13.0408382 -5.6848527 0.0000000 -0.0217686 0.0000000 0.0000000 -0.0021425 0.0000000 - 3 -12.5269876 -13.0408382 -13.3380146 -8.5018719 0.0000000 -0.1409874 0.0000000 0.0000000 -0.0767474 0.0000000 - 4 -5.4491024 -5.6848527 -8.5018719 -7.7470598 0.0000000 -0.1604258 0.0000000 0.0000000 -0.2004001 0.0000000 - 5 0.0000000 0.0000000 0.0000000 0.0000000 -11.7587263 -0.0000000 -0.0000000 -3.8867328 -0.0000000 -0.0000000 - 6 -0.0187383 -0.0217686 -0.1409874 -0.1604258 -0.0000000 -11.7247201 0.0000000 -0.0000000 -3.8538235 0.0000000 - 7 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -11.6714398 -0.0000000 0.0000000 -3.8022619 - 8 0.0000000 0.0000000 0.0000000 0.0000000 -3.8867328 -0.0000000 -0.0000000 -4.8575277 -0.0000000 -0.0000000 - 9 -0.0030616 -0.0021425 -0.0767474 -0.2004001 -0.0000000 -3.8538235 0.0000000 -0.0000000 -4.7808320 0.0000000 - 10 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -3.8022619 -0.0000000 0.0000000 -4.6606664 - 11 -0.5421367 -0.5620824 -1.4779068 -2.2377454 -1.5650189 -1.2380611 0.0000000 -2.3209862 -1.8321763 0.0000000 - 12 -1.8162218 -1.8919912 -3.3424749 -3.9493127 -1.1877301 -0.9927874 0.0000000 -2.0249359 -1.6873298 0.0000000 - 13 -0.5421367 -0.5620824 -1.4779068 -2.2377454 1.5650189 -1.2380611 0.0000000 2.3209862 -1.8321763 0.0000000 - 14 -1.8162218 -1.8919912 -3.3424749 -3.9493127 1.1877301 -0.9927874 0.0000000 2.0249359 -1.6873298 0.0000000 - - 11 12 13 14 - - 1 -0.5421367 -1.8162218 -0.5421367 -1.8162218 - 2 -0.5620824 -1.8919912 -0.5620824 -1.8919912 - 3 -1.4779068 -3.3424749 -1.4779068 -3.3424749 - 4 -2.2377454 -3.9493127 -2.2377454 -3.9493127 - 5 -1.5650189 -1.1877301 1.5650189 1.1877301 - 6 -1.2380611 -0.9927874 -1.2380611 -0.9927874 - 7 0.0000000 0.0000000 0.0000000 0.0000000 - 8 -2.3209862 -2.0249359 2.3209862 2.0249359 - 9 -1.8321763 -1.6873298 -1.8321763 -1.6873298 - 10 0.0000000 0.0000000 0.0000000 0.0000000 - 11 -5.8164327 -3.6034799 -0.1504914 -0.9123138 - 12 -3.6034799 -4.5175558 -0.9123138 -2.1254973 - 13 -0.1504914 -0.9123138 -5.8164327 -3.6034799 - 14 -0.9123138 -2.1254973 -3.6034799 -4.5175558 - - Core Hamiltonian: - - 1 2 3 4 5 6 7 8 9 10 - - 1 -29.8841477 -32.1509650 -11.6930374 -5.3183614 0.0000000 -0.0187383 0.0000000 0.0000000 -0.0030616 0.0000000 - 2 -32.1509650 -26.0783945 -11.9316834 -5.5236989 0.0000000 -0.0217686 0.0000000 0.0000000 -0.0021425 0.0000000 - 3 -11.6930374 -11.9316834 -11.9283146 -7.9930322 0.0000000 -0.1409874 0.0000000 0.0000000 -0.0767474 0.0000000 - 4 -5.3183614 -5.5236989 -7.9930322 -7.3201598 0.0000000 -0.1604258 0.0000000 0.0000000 -0.2004001 0.0000000 - 5 0.0000000 0.0000000 0.0000000 0.0000000 -8.1237488 0.0000000 -0.0000000 -3.4544388 0.0000000 -0.0000000 - 6 -0.0187383 -0.0217686 -0.1409874 -0.1604258 0.0000000 -8.0897426 0.0000000 0.0000000 -3.4215295 0.0000000 - 7 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -8.0364623 -0.0000000 0.0000000 -3.3699679 - 8 0.0000000 0.0000000 0.0000000 0.0000000 -3.4544388 0.0000000 -0.0000000 -4.3232777 0.0000000 0.0000000 - 9 -0.0030616 -0.0021425 -0.0767474 -0.2004001 0.0000000 -3.4215295 0.0000000 0.0000000 -4.2465820 0.0000000 - 10 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -3.3699679 0.0000000 0.0000000 -4.1264164 - 11 -0.5645415 -0.5904030 -1.5170275 -2.1531108 -1.4561432 -1.1529982 0.0000000 -2.0710925 -1.6369379 0.0000000 - 12 -1.8018352 -1.8749860 -3.2587555 -3.8148856 -1.1001179 -0.9243373 0.0000000 -1.8436313 -1.5456791 0.0000000 - 13 -0.5645415 -0.5904030 -1.5170275 -2.1531108 1.4561432 -1.1529982 0.0000000 2.0710925 -1.6369379 0.0000000 - 14 -1.8018352 -1.8749860 -3.2587555 -3.8148856 1.1001179 -0.9243373 0.0000000 1.8436313 -1.5456791 0.0000000 - - 11 12 13 14 - - 1 -0.5645415 -1.8018352 -0.5645415 -1.8018352 - 2 -0.5904030 -1.8749860 -0.5904030 -1.8749860 - 3 -1.5170275 -3.2587555 -1.5170275 -3.2587555 - 4 -2.1531108 -3.8148856 -2.1531108 -3.8148856 - 5 -1.4561432 -1.1001179 1.4561432 1.1001179 - 6 -1.1529982 -0.9243373 -1.1529982 -0.9243373 - 7 0.0000000 0.0000000 0.0000000 0.0000000 - 8 -2.0710925 -1.8436313 2.0710925 1.8436313 - 9 -1.6369379 -1.5456791 -1.6369379 -1.5456791 - 10 0.0000000 0.0000000 0.0000000 0.0000000 - 11 -4.4007067 -3.3109060 -0.1806462 -0.9135341 - 12 -3.3109060 -4.2511558 -0.9135341 -2.0880454 - 13 -0.1806462 -0.9135341 -4.4007067 -3.3109060 - 14 -0.9135341 -2.0880454 -3.3109060 -4.2511558 - - S^-1/2 Matrix: - - 1 2 3 4 5 6 7 8 9 10 - - 1 1.6168477 -0.8735857 -0.0168557 -0.0400834 -0.0000000 0.0007849 -0.0000000 0.0000000 -0.0066718 -0.0000000 - 2 -0.8735857 1.7126985 -0.3425777 0.1530403 0.0000000 -0.0036593 -0.0000000 -0.0000000 0.0205187 0.0000000 - 3 -0.0168557 -0.3425777 1.7188396 -1.0453853 0.0000000 0.0195869 0.0000000 -0.0000000 -0.1493327 -0.0000000 - 4 -0.0400834 0.1530403 -1.0453853 2.3990204 0.0000000 -0.0468349 -0.0000000 -0.0000000 0.4752549 0.0000000 - 5 -0.0000000 0.0000000 0.0000000 0.0000000 1.1353389 -0.0000000 0.0000000 -0.3602418 0.0000000 0.0000000 - 6 0.0007849 -0.0036593 0.0195869 -0.0468349 -0.0000000 1.1252613 0.0000000 0.0000000 -0.3202069 0.0000000 - 7 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 1.1188213 -0.0000000 -0.0000000 -0.3039525 - 8 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.3602418 0.0000000 -0.0000000 1.7016622 -0.0000000 -0.0000000 - 9 -0.0066718 0.0205187 -0.1493327 0.4752549 0.0000000 -0.3202069 -0.0000000 -0.0000000 1.3744671 0.0000000 - 10 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 -0.3039525 -0.0000000 0.0000000 1.1188213 - 11 0.0028695 -0.0006931 0.0570819 -0.1528879 -0.0510625 -0.0335967 0.0000000 -0.1330073 -0.1599999 -0.0000000 - 12 0.0062783 -0.0255487 0.1362283 -0.6090154 0.0868699 0.0388408 0.0000000 -0.6127885 -0.2763531 0.0000000 - 13 0.0028695 -0.0006931 0.0570819 -0.1528879 0.0510625 -0.0335967 -0.0000000 0.1330073 -0.1599999 0.0000000 - 14 0.0062783 -0.0255487 0.1362283 -0.6090154 -0.0868699 0.0388408 0.0000000 0.6127885 -0.2763531 -0.0000000 - - 11 12 13 14 - - 1 0.0028695 0.0062783 0.0028695 0.0062783 - 2 -0.0006931 -0.0255487 -0.0006931 -0.0255487 - 3 0.0570819 0.1362283 0.0570819 0.1362283 - 4 -0.1528879 -0.6090154 -0.1528879 -0.6090154 - 5 -0.0510625 0.0868699 0.0510625 -0.0868699 - 6 -0.0335967 0.0388408 -0.0335967 0.0388408 - 7 0.0000000 0.0000000 -0.0000000 0.0000000 - 8 -0.1330073 -0.6127885 0.1330073 0.6127885 - 9 -0.1599999 -0.2763531 -0.1599999 -0.2763531 - 10 -0.0000000 0.0000000 0.0000000 -0.0000000 - 11 1.3434367 -0.4177307 0.0277612 0.0503384 - 12 -0.4177307 1.9127448 0.0503384 -0.3714478 - 13 0.0277612 0.0503384 1.3434367 -0.4177307 - 14 0.0503384 -0.3714478 -0.4177307 1.9127448 - - Initial F' Matrix: - - 1 2 3 4 5 6 7 8 9 10 - - 1 -6.6695586 -29.7173637 -0.3454939 -1.9567322 0.0000000 0.0215839 0.0000000 -0.0000000 -0.1606919 0.0000000 - 2 -29.7173637 1.8073831 -4.5435902 0.5717244 0.0000000 -0.0185604 0.0000000 -0.0000000 0.1586191 0.0000000 - 3 -0.3454939 -4.5435902 -8.2506270 -1.8091409 -0.0000000 -0.1182732 -0.0000000 0.0000000 0.0255967 0.0000000 - 4 -1.9567322 0.5717244 -1.8091409 -4.3301947 0.0000000 0.0042797 0.0000000 0.0000000 0.0532702 -0.0000000 - 5 0.0000000 0.0000000 -0.0000000 0.0000000 -8.2368708 0.0000000 -0.0000000 -0.2827735 -0.0000000 -0.0000000 - 6 0.0215839 -0.0185604 -0.1182732 0.0042797 0.0000000 -8.1929015 -0.0000000 -0.0000000 -0.3607691 -0.0000000 - 7 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 -8.1489194 0.0000000 0.0000000 -0.3935247 - 8 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.2827735 -0.0000000 0.0000000 -3.5788198 0.0000000 0.0000000 - 9 -0.1606919 0.1586191 0.0255967 0.0532702 -0.0000000 -0.3607691 0.0000000 0.0000000 -3.5619183 -0.0000000 - 10 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.3935247 0.0000000 -0.0000000 -3.6157135 - 11 0.0020265 0.0017528 -0.0668127 -0.2444342 -0.1410080 -0.1086926 -0.0000000 -0.2608318 -0.2352070 0.0000000 - 12 -0.0024477 -0.3758020 -0.3811658 -0.6078198 -0.2454745 -0.1505151 -0.0000000 -0.1332617 -0.0948509 -0.0000000 - 13 0.0020265 0.0017528 -0.0668127 -0.2444342 0.1410080 -0.1086926 0.0000000 0.2608318 -0.2352070 0.0000000 - 14 -0.0024477 -0.3758020 -0.3811658 -0.6078198 0.2454745 -0.1505151 -0.0000000 0.1332617 -0.0948509 0.0000000 - - 11 12 13 14 - - 1 0.0020265 -0.0024477 0.0020265 -0.0024477 - 2 0.0017528 -0.3758020 0.0017528 -0.3758020 - 3 -0.0668127 -0.3811658 -0.0668127 -0.3811658 - 4 -0.2444342 -0.6078198 -0.2444342 -0.6078198 - 5 -0.1410080 -0.2454745 0.1410080 0.2454745 - 6 -0.1086926 -0.1505151 -0.1086926 -0.1505151 - 7 -0.0000000 -0.0000000 0.0000000 -0.0000000 - 8 -0.2608318 -0.1332617 0.2608318 0.1332617 - 9 -0.2352070 -0.0948509 -0.2352070 -0.0948509 - 10 0.0000000 -0.0000000 0.0000000 0.0000000 - 11 -3.7670960 -0.5152751 0.0714565 -0.0157822 - 12 -0.5152751 -2.6631507 -0.0157822 -0.2547049 - 13 0.0714565 -0.0157822 -3.7670960 -0.5152751 - 14 -0.0157822 -0.2547049 -0.5152751 -2.6631507 - - Initial C Matrix: - - 1 2 3 4 5 6 7 8 9 10 - - 1 0.6280732 0.2258886 0.0000000 0.0605171 -0.0000000 -0.0915078 0.0000000 -0.0604184 0.0000000 -0.0000000 - 2 0.4292397 0.2021183 0.0000000 0.0514855 -0.0000000 -0.0784796 0.0000000 -0.0517677 0.0000000 -0.0000000 - 3 -0.0512602 -1.2218028 -0.0000000 -0.3098082 0.0000000 1.0367575 -0.0000000 0.8088599 -0.0000000 0.0000000 - 4 0.0285796 0.2678803 -0.0000000 0.0106576 0.0000000 -1.3518974 0.0000000 -1.2111249 0.0000000 -0.0000000 - 5 -0.0000000 -0.0000000 -1.1083318 0.0000000 -0.0000000 -0.0000000 -0.3228585 0.0000000 -0.0000000 -0.3087369 - 6 -0.0000129 -0.2888995 0.0000000 1.0550998 -0.0000000 0.1797043 -0.0000000 -0.2981431 -0.0000000 0.0000000 - 7 -0.0000000 -0.0000000 -0.0000000 0.0000000 1.0885977 -0.0000000 0.0000000 -0.0000000 -0.3988776 0.0000000 - 8 0.0000000 0.0000000 0.3121492 -0.0000000 0.0000000 -0.0000000 0.5273485 -0.0000000 0.0000000 1.6515151 - 9 0.0047188 0.1053383 -0.0000000 -0.2141580 0.0000000 -0.3714148 0.0000000 0.6175432 0.0000000 -0.0000000 - 10 0.0000000 0.0000000 0.0000000 -0.0000000 -0.2067832 -0.0000000 -0.0000000 0.0000000 1.1407844 -0.0000000 - 11 -0.0007873 -0.0123031 0.0279490 -0.0195130 -0.0000000 -0.3129911 0.6070743 0.4057711 -0.0000000 -0.5481735 - 12 -0.0057923 -0.0619227 -0.1325008 0.0375542 -0.0000000 0.1679731 -0.1704577 -0.0117229 -0.0000000 -0.5320213 - 13 -0.0007873 -0.0123031 -0.0279490 -0.0195130 -0.0000000 -0.3129911 -0.6070743 0.4057711 -0.0000000 0.5481735 - 14 -0.0057923 -0.0619227 0.1325008 0.0375542 0.0000000 0.1679731 0.1704577 -0.0117229 0.0000000 0.5320213 - - 11 12 13 14 - - 1 -0.0343412 -0.0344830 0.0000000 1.7075782 - 2 -0.0329348 -0.0264815 0.0000000 -1.8975340 - 3 0.6543159 0.5134953 -0.0000000 0.4678272 - 4 -1.4142202 -1.5395765 0.0000000 -0.3902718 - 5 0.0000000 -0.0000000 -0.1054536 -0.0000000 - 6 0.2347642 0.0590622 0.0000000 0.0112865 - 7 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 8 -0.0000000 0.0000000 0.8418990 0.0000000 - 9 -1.2781883 -0.4779373 -0.0000000 -0.0760753 - 10 0.0000000 -0.0000000 0.0000000 -0.0000000 - 11 0.7742269 -0.4451615 0.5705517 0.0144339 - 12 0.2935030 1.2633109 -1.6648451 0.0871055 - 13 0.7742269 -0.4451615 -0.5705517 0.0144339 - 14 0.2935030 1.2633109 1.6648451 0.0871055 - - Initial Density Matrix: - - 1 2 3 4 5 6 7 8 9 10 - - 1 0.4491640 0.3183659 -0.3269352 0.0791062 -0.0000000 -0.0014156 -0.0000000 0.0000000 0.0137982 0.0000000 - 2 0.3183659 0.2277493 -0.2849023 0.0669597 -0.0000000 -0.0040751 -0.0000000 0.0000000 0.0122902 0.0000000 - 3 -0.3269352 -0.2849023 1.5914109 -0.3320638 0.0000000 0.0261003 0.0000000 -0.0000000 -0.0625966 -0.0000000 - 4 0.0791062 0.0669597 -0.3320638 0.0726902 -0.0000000 -0.0661460 0.0000000 0.0000000 0.0260705 -0.0000000 - 5 -0.0000000 -0.0000000 0.0000000 -0.0000000 1.2283995 -0.0000000 -0.0000000 -0.3459649 0.0000000 0.0000000 - 6 -0.0014156 -0.0040751 0.0261003 -0.0661460 -0.0000000 1.1966985 -0.0000000 0.0000000 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-0.0038292 -0.0130685 - 3 0.0211176 0.0643197 0.0211176 0.0643197 - 4 -0.0035262 -0.0163532 -0.0035262 -0.0163532 - 5 -0.0309767 0.1468549 0.0309767 -0.1468549 - 6 -0.0170338 0.0575130 -0.0170338 0.0575130 - 7 -0.0000000 -0.0000000 -0.0000000 0.0000000 - 8 0.0087242 -0.0413600 -0.0087242 0.0413600 - 9 0.0028792 -0.0145927 0.0028792 -0.0145927 - 10 0.0000000 0.0000000 0.0000000 -0.0000000 - 11 0.0013139 -0.0036697 -0.0002484 0.0037369 - 12 -0.0036697 0.0228348 0.0037369 -0.0122782 - 13 -0.0002484 0.0037369 0.0013139 -0.0036697 - 14 0.0037369 -0.0122782 -0.0036697 0.0228348 - - - Iter E(elec) E(tot) Delta(E) RMS(D) - 00 -132.798981914282 -124.796614852471 - - Fock Matrix: - - 1 2 3 4 5 6 7 8 9 10 - - 1 -12.9345791 -19.1805975 -7.2302977 -3.2823695 0.0000000 -0.0179180 0.0000000 -0.0000000 -0.0032220 0.0000000 - 2 -19.1805975 -10.8142636 -6.0048818 -2.9466986 0.0000000 -0.0212920 0.0000000 0.0000000 -0.0024868 0.0000000 - 3 -7.2302977 -6.0048818 -2.3555669 -1.4597105 -0.0000000 -0.1414377 0.0000000 0.0000000 -0.0786739 0.0000000 - 4 -3.2823695 -2.9466986 -1.4597105 -0.6272387 0.0000000 -0.1626753 0.0000000 0.0000000 -0.2033920 0.0000000 - 5 0.0000000 0.0000000 -0.0000000 0.0000000 1.0871062 0.0000000 -0.0000000 -0.0141120 -0.0000000 -0.0000000 - 6 -0.0179180 -0.0212920 -0.1414377 -0.1626753 0.0000000 1.1228012 -0.0000000 -0.0000000 0.0166637 -0.0000000 - 7 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 1.1776804 -0.0000000 -0.0000000 0.0690468 - 8 -0.0000000 0.0000000 0.0000000 0.0000000 -0.0141120 -0.0000000 -0.0000000 0.3759397 -0.0000000 -0.0000000 - 9 -0.0032220 -0.0024868 -0.0786739 -0.2033920 -0.0000000 0.0166637 -0.0000000 -0.0000000 0.4514739 -0.0000000 - 10 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 0.0690468 -0.0000000 -0.0000000 0.5722572 - 11 -0.3496285 -0.3419488 -0.3493378 -0.2354052 -0.1291556 -0.1164503 0.0000000 -0.0411344 -0.0515846 0.0000000 - 12 -1.1130468 -1.0222617 -0.6461677 -0.3190412 -0.0541921 -0.1090654 0.0000000 0.0694961 -0.0528832 0.0000000 - 13 -0.3496285 -0.3419488 -0.3493378 -0.2354052 0.1291556 -0.1164503 0.0000000 0.0411344 -0.0515846 0.0000000 - 14 -1.1130468 -1.0222617 -0.6461677 -0.3190412 0.0541921 -0.1090654 0.0000000 -0.0694961 -0.0528832 0.0000000 - - 11 12 13 14 - - 1 -0.3496285 -1.1130468 -0.3496285 -1.1130468 - 2 -0.3419488 -1.0222617 -0.3419488 -1.0222617 - 3 -0.3493378 -0.6461677 -0.3493378 -0.6461677 - 4 -0.2354052 -0.3190412 -0.2354052 -0.3190412 - 5 -0.1291556 -0.0541921 0.1291556 0.0541921 - 6 -0.1164503 -0.1090654 -0.1164503 -0.1090654 - 7 0.0000000 0.0000000 0.0000000 0.0000000 - 8 -0.0411344 0.0694961 0.0411344 -0.0694961 - 9 -0.0515846 -0.0528832 -0.0515846 -0.0528832 - 10 0.0000000 0.0000000 0.0000000 0.0000000 - 11 0.2964628 -0.1937347 -0.0552060 -0.1243929 - 12 -0.1937347 -0.1126352 -0.1243929 -0.1707662 - 13 -0.0552060 -0.1243929 0.2964628 -0.1937347 - 14 -0.1243929 -0.1707662 -0.1937347 -0.1126352 - 01 -68.850894452772 -60.848527390961 63.948087461510 4.935281701149 - 02 -95.901449040118 -87.899081978308 -27.050554587346 4.345238332117 - 03 -74.587586343951 -66.585219282140 21.313862696167 2.145005122635 - 04 -91.278668433461 -83.276301371651 -16.691082089510 1.819741256945 - 05 -78.537184444565 -70.534817382754 12.741483988896 1.092752792730 - 06 -87.998977364322 -79.996610302511 -9.461792919757 0.850372902576 - 07 -81.091202826782 -73.088835764971 6.907774537540 0.571304030605 - 08 -86.060052070328 -78.057685008518 -4.968849243547 0.424707736617 - 09 -82.504507711263 -74.502140649453 3.555544359065 0.292101938147 - 10 -85.030906363244 -77.028539301434 -2.526398651981 0.212115172680 - 11 -83.237393342602 -75.235026280792 1.793513020642 0.147459722939 - 12 -84.506844987724 -76.504477925914 -1.269451645122 0.105765110366 - 13 -83.608159340229 -75.605792278418 0.898685647495 0.074033606064 - 14 -84.243585050153 -76.241217988343 -0.635425709924 0.052749265023 - 15 -83.794164746828 -75.791797685018 0.449420303325 0.037080965857 - 16 -84.111858514967 -76.109491453156 -0.317693768138 0.026325546039 - 17 -83.887232465023 -75.884865403212 0.224626049944 0.018552042038 - 18 -84.046015331432 -76.043648269622 -0.158782866410 0.013145253229 - 19 -83.933760325346 -75.931393263535 0.112255006087 0.009276668654 - 20 -84.013111664155 -76.010744602344 -0.079351338809 0.006566094412 - 21 -83.957015055900 -75.954647994089 0.056096608255 0.004637318527 - 22 -83.996669432447 -75.994302370637 -0.039654376548 0.003280428910 - 23 -83.968636747708 -75.966269685898 0.028032684739 0.002317794031 - 24 -83.988453084451 -75.986086022640 -0.019816336742 0.001639086735 - 25 -83.974444550703 -75.972077488893 0.014008533748 0.001158368239 - 26 -83.984347256722 -75.981980194912 -0.009902706019 0.000819029487 - 27 -83.977346886630 -75.974979824819 0.007000370093 0.000578893795 - 28 -83.982295501589 -75.979928439779 -0.004948614960 0.000409271487 - 29 -83.978797261530 -75.976430199719 0.003498240059 0.000289294748 - 30 -83.981270198772 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0.000000012386 - 59 -83.980245993340 -75.977878931530 0.000000105873 0.000000008756 - 60 -83.980246068183 -75.977879006372 -0.000000074843 0.000000006190 - 61 -83.980246015276 -75.977878953465 0.000000052907 0.000000004375 - 62 -83.980246052676 -75.977878990866 -0.000000037401 0.000000003093 - 63 -83.980246026237 -75.977878964427 0.000000026439 0.000000002187 - 64 -83.980246044927 -75.977878983117 -0.000000018690 0.000000001546 - 65 -83.980246031715 -75.977878969905 0.000000013212 0.000000001093 - 66 -83.980246041055 -75.977878979244 -0.000000009340 0.000000000772 - 67 -83.980246034453 -75.977878972642 0.000000006602 0.000000000546 - 68 -83.980246039120 -75.977878977309 -0.000000004667 0.000000000386 - 69 -83.980246035821 -75.977878974010 0.000000003299 0.000000000273 - 70 -83.980246038153 -75.977878976342 -0.000000002332 0.000000000193 - 71 -83.980246036504 -75.977878974694 0.000000001649 0.000000000136 - 72 -83.980246037670 -75.977878975859 -0.000000001165 0.000000000096 - 73 -83.980246036846 -75.977878975035 0.000000000824 0.000000000068 - 74 -83.980246037428 -75.977878975618 -0.000000000582 0.000000000048 - 75 -83.980246037016 -75.977878975206 0.000000000412 0.000000000034 - 76 -83.980246037308 -75.977878975497 -0.000000000291 0.000000000024 - 77 -83.980246037102 -75.977878975291 0.000000000206 0.000000000017 - 78 -83.980246037247 -75.977878975437 -0.000000000145 0.000000000012 - 79 -83.980246037144 -75.977878975334 0.000000000103 0.000000000008 - 80 -83.980246037217 -75.977878975406 -0.000000000072 0.000000000006 - 81 -83.980246037166 -75.977878975355 0.000000000051 0.000000000004 - 82 -83.980246037202 -75.977878975391 -0.000000000036 0.000000000003 - 83 -83.980246037176 -75.977878975366 0.000000000026 0.000000000002 - 84 -83.980246037194 -75.977878975384 -0.000000000018 0.000000000001 - 85 -83.980246037182 -75.977878975371 0.000000000013 0.000000000001 - 86 -83.980246037191 -75.977878975380 -0.000000000009 0.000000000001 - 87 -83.980246037184 -75.977878975374 0.000000000006 0.000000000001 - 88 -83.980246037189 -75.977878975378 -0.000000000005 0.000000000000 - 89 -83.980246037186 -75.977878975375 0.000000000003 0.000000000000 - 90 -83.980246037188 -75.977878975377 -0.000000000002 0.000000000000 - 91 -83.980246037186 -75.977878975376 0.000000000001 0.000000000000 - 92 -83.980246037187 -75.977878975377 -0.000000000001 0.000000000000 - - 1 2 3 4 5 6 7 8 9 10 - - 1 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0657570 0.0000000 -0.0000000 -0.0107439 -0.0000000 -0.0000000 - 2 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0763908 0.0000000 -0.0000000 -0.0075187 0.0000000 -0.0000000 - 3 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.4955483 0.0000000 -0.0000000 -0.2744942 0.0000000 0.0000000 - 4 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.5785246 -0.0000000 0.0000000 -0.9135863 0.0000000 0.0000000 - 5 -0.0657570 -0.0763908 -0.4955483 -0.5785246 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 - 6 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 7 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 - 8 -0.0107439 -0.0075187 -0.2744942 -0.9135863 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 - 9 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 10 -0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 - 11 -0.0033167 -0.0021022 -0.1122107 -0.3994378 -0.2478997 -0.1240176 0.0000000 -0.7172015 -0.4204084 0.0000000 - 12 -0.0028978 -0.0019569 -0.0853768 -0.3765106 -0.3221755 -0.0361937 0.0000000 -1.1058828 -0.2608900 0.0000000 - 13 0.0033167 0.0021022 0.1122107 0.3994378 -0.2478997 0.1240176 -0.0000000 -0.7172015 0.4204084 -0.0000000 - 14 0.0028978 0.0019569 0.0853768 0.3765106 -0.3221755 0.0361937 -0.0000000 -1.1058828 0.2608900 -0.0000000 - - 11 12 13 14 - - 1 -0.0033167 -0.0028978 0.0033167 0.0028978 - 2 -0.0021022 -0.0019569 0.0021022 0.0019569 - 3 -0.1122107 -0.0853768 0.1122107 0.0853768 - 4 -0.3994378 -0.3765106 0.3994378 0.3765106 - 5 -0.2478997 -0.3221755 -0.2478997 -0.3221755 - 6 -0.1240176 -0.0361937 0.1240176 0.0361937 - 7 0.0000000 0.0000000 -0.0000000 -0.0000000 - 8 -0.7172015 -1.1058828 -0.7172015 -1.1058828 - 9 -0.4204084 -0.2608900 0.4204084 0.2608900 - 10 0.0000000 0.0000000 -0.0000000 -0.0000000 - 11 -1.6380368 -1.1188778 0.0000000 -0.1454915 - 12 -1.1188778 -1.6380368 0.1454915 0.0000000 - 13 0.0000000 0.1454915 1.6380368 1.1188778 - 14 -0.1454915 0.0000000 1.1188778 1.6380368 - - 1 2 3 4 5 6 7 8 9 10 - - 1 0.3572894 0.2951712 -0.0775093 -0.0747510 -0.0000000 0.0149199 -0.0000000 0.0000000 0.0090562 -0.0000000 - 2 0.2951712 0.2503195 -0.1071597 -0.1042236 -0.0000000 0.0205469 -0.0000000 0.0000000 0.0128980 -0.0000000 - 3 -0.0775093 -0.1071597 0.3046369 0.3004449 0.0000000 -0.0668819 0.0000000 -0.0000000 -0.0427649 0.0000000 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0.0272982 0.0174518 -0.1284597 0.0987376 -0.0000000 -0.0501619 0.0516650 -0.0000000 - 14 0.0023064 0.0033119 -0.0113312 -0.0165866 -0.0874269 0.0623219 -0.0000000 -0.0341391 0.0332972 -0.0000000 - - 11 12 13 14 - - 1 -0.0077236 0.0023064 -0.0077236 0.0023064 - 2 -0.0105986 0.0033119 -0.0105986 0.0033119 - 3 0.0272982 -0.0113312 0.0272982 -0.0113312 - 4 0.0174518 -0.0165866 0.0174518 -0.0165866 - 5 0.1284597 0.0874269 -0.1284597 -0.0874269 - 6 0.0987376 0.0623219 0.0987376 0.0623219 - 7 -0.0000000 0.0000000 -0.0000000 -0.0000000 - 8 0.0501619 0.0341391 -0.0501619 -0.0341391 - 9 0.0516650 0.0332972 0.0516650 0.0332972 - 10 -0.0000000 0.0000000 -0.0000000 -0.0000000 - 11 0.0859661 0.0525323 -0.0207747 -0.0201132 - 12 0.0525323 0.0349829 -0.0201132 -0.0144580 - 13 -0.0207747 -0.0201132 0.0859661 0.0525323 - 14 -0.0201132 -0.0144580 0.0525323 0.0349829 - -Mu-X = 0.000000000000 -Mu-Y = 1.070995737060 -Mu-Z = 0.000000000000 -Total dipole moment (au) = 1.070995737060 - -Charge on atom 0: 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RMS(D) - 00 -133.418270737355 -125.415903675545 - - Fock Matrix: - - 1 2 3 4 5 6 7 8 9 10 - - 1 -12.5313716 -18.8531119 -7.1133621 -3.2296385 -0.0000000 -0.0158213 -0.0000000 -0.0000000 -0.0032668 -0.0000000 - 2 -18.8531119 -10.4457415 -5.8776298 -2.8926916 -0.0000000 -0.0112568 -0.0000000 -0.0000000 -0.0018698 -0.0000000 - 3 -7.1133621 -5.8776298 -2.2106664 -1.3572029 0.0000000 -0.1080384 -0.0000000 0.0000000 -0.0704556 -0.0000000 - 4 -3.2296385 -2.8926916 -1.3572029 -0.5452207 0.0000000 -0.1375780 -0.0000000 0.0000000 -0.1836552 -0.0000000 - 5 -0.0000000 -0.0000000 0.0000000 0.0000000 1.2177641 -0.0000000 -0.0000000 0.0284236 0.0000000 -0.0000000 - 6 -0.0158213 -0.0112568 -0.1080384 -0.1375780 -0.0000000 1.2551387 -0.0000000 0.0000000 0.0570347 -0.0000000 - 7 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 1.3143187 -0.0000000 -0.0000000 0.1002487 - 8 -0.0000000 -0.0000000 0.0000000 0.0000000 0.0284236 0.0000000 -0.0000000 0.3941355 0.0000000 -0.0000000 - 9 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-0.0073742 -0.0110250 - 6 0.0043208 0.0000000 0.0000000 0.0199496 -0.0000000 -0.0047579 0.0968761 0.0747530 -0.0130152 0.0028914 - 7 0.0000000 0.0000000 0.0000000 0.0000000 0.0266204 -0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 - 8 -0.0000000 0.0120877 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0451677 0.0356238 -0.0028000 -0.0041862 - 9 0.0020093 0.0000000 0.0000000 0.0097954 -0.0000000 -0.0023172 0.0457154 0.0362476 -0.0060120 0.0017243 - 10 0.0000000 0.0000000 0.0000000 0.0000000 0.0143847 -0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 - 11 0.0000793 -0.0000000 0.0000000 0.0002366 0.0000000 -0.0000603 0.0016007 0.0009964 -0.0002468 -0.0000405 - 12 -0.0000000 0.0033216 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0124116 0.0097890 -0.0007694 -0.0011503 - 13 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 - 14 0.0002366 0.0000000 0.0000000 0.0010551 -0.0000000 -0.0002519 0.0052432 0.0039812 -0.0007129 0.0001327 - 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0.0002468 -0.0007694 0.0000000 0.0007129 -0.0000000 -0.0001872 0.0021299 0.0007870 -0.0006023 0.0001168 - 25 -0.0000405 0.0011503 -0.0000000 0.0001327 0.0000000 -0.0000188 0.0037870 0.0036004 -0.0001168 -0.0001897 - 26 0.0000000 0.0000000 0.0000000 0.0000000 0.0008498 -0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 - - 21 22 23 24 25 26 - - 1 0.0000000 -0.0083975 -0.0003991 -0.0020500 0.0020744 0.0000000 - 2 -0.0000000 -0.0113196 -0.0003451 -0.0027291 0.0028269 0.0000000 - 3 0.0000000 0.0329877 0.0013460 0.0076571 -0.0079424 0.0000000 - 4 0.0000000 0.0045763 -0.0169209 0.0033508 -0.0074364 0.0000000 - 5 0.0000000 -0.1189548 -0.0938199 -0.0073742 0.0110250 0.0000000 - 6 -0.0000000 0.0968761 0.0747530 0.0130152 0.0028914 0.0000000 - 7 0.0169507 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0169507 - 8 0.0000000 -0.0451677 -0.0356238 -0.0028000 0.0041862 0.0000000 - 9 -0.0000000 0.0457154 0.0362476 0.0060120 0.0017243 0.0000000 - 10 0.0091596 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0091596 - 11 0.0000000 0.0016007 0.0009964 0.0002468 -0.0000405 0.0000000 - 12 0.0000000 -0.0124116 -0.0097890 -0.0007694 0.0011503 0.0000000 - 13 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 14 0.0000000 0.0052432 0.0039812 0.0007129 0.0001327 0.0000000 - 15 0.0008498 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0008498 - 16 -0.0000000 -0.0013358 -0.0009742 -0.0001872 -0.0000188 -0.0000000 - 17 0.0000000 -0.0131658 -0.0150089 0.0021299 0.0037870 0.0000000 - 18 0.0000000 -0.0150089 -0.0133765 0.0007870 0.0036004 0.0000000 - 19 -0.0000000 -0.0021299 -0.0007870 -0.0006023 -0.0001168 -0.0000000 - 20 -0.0000000 0.0037870 0.0036004 0.0001168 -0.0001897 -0.0000000 - 21 0.0005411 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0005411 - 22 -0.0000000 0.0795900 0.0581478 0.0078800 -0.0048098 -0.0000000 - 23 -0.0000000 0.0581478 0.0443223 0.0053221 -0.0031800 -0.0000000 - 24 -0.0000000 0.0078800 0.0053221 0.0009587 -0.0004161 0.0000000 - 25 0.0000000 -0.0048098 -0.0031800 -0.0004161 0.0006071 0.0000000 - 26 0.0005411 -0.0000000 -0.0000000 0.0000000 0.0000000 0.0005411 - -Mu-X = 0.000000000000 -Mu-Y = 0.902662444474 -Mu-Z = -0.000000000000 -Total dipole moment (au) = 0.902662444474 - -Charge on atom 0: -0.610994680041 -Charge on atom 1: 0.305497340021 -Charge on atom 2: 0.305497340021 diff --git a/Project#03/output/h2o/STO-3G/output.txt b/Project#03/output/h2o/STO-3G/output.txt deleted file mode 100644 index 3fc4984..0000000 --- a/Project#03/output/h2o/STO-3G/output.txt +++ /dev/null @@ -1,177 +0,0 @@ - -Nuclear repulsion energy = 8.0023670618 - - Overlap Integrals: - - 1 2 3 4 5 6 7 - - 1 1.0000000 0.2367039 -0.0000000 -0.0000000 -0.0000000 0.0384056 0.0384056 - 2 0.2367039 1.0000000 0.0000000 -0.0000000 0.0000000 0.3861388 0.3861388 - 3 -0.0000000 0.0000000 1.0000000 -0.0000000 0.0000000 0.2684382 -0.2684382 - 4 -0.0000000 -0.0000000 -0.0000000 1.0000000 -0.0000000 0.2097269 0.2097269 - 5 -0.0000000 0.0000000 0.0000000 -0.0000000 1.0000000 -0.0000000 -0.0000000 - 6 0.0384056 0.3861388 0.2684382 0.2097269 -0.0000000 1.0000000 0.1817599 - 7 0.0384056 0.3861388 -0.2684382 0.2097269 -0.0000000 0.1817599 1.0000000 - - Kinetic-Energy Integrals: - - 1 2 3 4 5 6 7 - - 1 29.0031999 -0.1680109 0.0000000 0.0000000 -0.0000000 -0.0084164 -0.0084164 - 2 -0.1680109 0.8081280 0.0000000 -0.0000000 0.0000000 0.0705174 0.0705174 - 3 0.0000000 0.0000000 2.5287312 -0.0000000 0.0000000 0.1470909 -0.1470909 - 4 0.0000000 -0.0000000 -0.0000000 2.5287312 -0.0000000 0.1149200 0.1149200 - 5 -0.0000000 0.0000000 0.0000000 -0.0000000 2.5287312 -0.0000000 -0.0000000 - 6 -0.0084164 0.0705174 0.1470909 0.1149200 -0.0000000 0.7600319 -0.0039799 - 7 -0.0084164 0.0705174 -0.1470909 0.1149200 -0.0000000 -0.0039799 0.7600319 - - Nuclear Attraction Integrals: - - 1 2 3 4 5 6 7 - - 1 -61.5805954 -7.4108219 0.0000000 -0.0144738 0.0000000 -1.2316859 -1.2316859 - 2 -7.4108219 -10.0090712 0.0000000 -0.1768902 0.0000000 -2.9772272 -2.9772272 - 3 0.0000000 0.0000000 -9.9875505 0.0000000 -0.0000000 -1.8222411 1.8222411 - 4 -0.0144738 -0.1768902 0.0000000 -9.9440430 0.0000000 -1.4717883 -1.4717883 - 5 0.0000000 0.0000000 -0.0000000 0.0000000 -9.8758761 0.0000000 0.0000000 - 6 -1.2316859 -2.9772272 -1.8222411 -1.4717883 0.0000000 -5.3002030 -1.0671660 - 7 -1.2316859 -2.9772272 1.8222411 -1.4717883 0.0000000 -1.0671660 -5.3002030 - - Core Hamiltonian: - - 1 2 3 4 5 6 7 - - 1 -32.5773954 -7.5788328 0.0000000 -0.0144738 0.0000000 -1.2401023 -1.2401023 - 2 -7.5788328 -9.2009433 0.0000000 -0.1768902 0.0000000 -2.9067098 -2.9067098 - 3 0.0000000 0.0000000 -7.4588193 0.0000000 0.0000000 -1.6751501 1.6751501 - 4 -0.0144738 -0.1768902 0.0000000 -7.4153118 0.0000000 -1.3568683 -1.3568683 - 5 0.0000000 0.0000000 0.0000000 0.0000000 -7.3471449 0.0000000 0.0000000 - 6 -1.2401023 -2.9067098 -1.6751501 -1.3568683 0.0000000 -4.5401711 -1.0711459 - 7 -1.2401023 -2.9067098 1.6751501 -1.3568683 0.0000000 -1.0711459 -4.5401711 - - S^-1/2 Matrix: - - 1 2 3 4 5 6 7 - - 1 1.0236346 -0.1368547 -0.0000000 -0.0074873 -0.0000000 0.0190279 0.0190279 - 2 -0.1368547 1.1578632 0.0000000 0.0721601 0.0000000 -0.2223326 -0.2223326 - 3 -0.0000000 0.0000000 1.0733148 0.0000000 -0.0000000 -0.1757583 0.1757583 - 4 -0.0074873 0.0721601 0.0000000 1.0383050 0.0000000 -0.1184626 -0.1184626 - 5 -0.0000000 0.0000000 -0.0000000 0.0000000 1.0000000 -0.0000000 -0.0000000 - 6 0.0190279 -0.2223326 -0.1757583 -0.1184626 -0.0000000 1.1297234 -0.0625975 - 7 0.0190279 -0.2223326 0.1757583 -0.1184626 -0.0000000 -0.0625975 1.1297234 - - Initial F' Matrix: - - 1 2 3 4 5 6 7 - - 1 -32.2545866 -2.7914909 -0.0000000 0.0086110 0.0000000 -0.1812967 -0.1812967 - 2 -2.7914909 -8.2368891 -0.0000000 -0.2282926 0.0000000 -0.3857987 -0.3857987 - 3 -0.0000000 -0.0000000 -7.5428890 -0.0000000 0.0000000 -0.1132121 0.1132121 - 4 0.0086110 -0.2282926 -0.0000000 -7.4570295 -0.0000000 -0.1102196 -0.1102196 - 5 0.0000000 0.0000000 0.0000000 -0.0000000 -7.3471449 0.0000000 0.0000000 - 6 -0.1812967 -0.3857987 -0.1132121 -0.1102196 0.0000000 -4.0329547 -0.0446466 - 7 -0.1812967 -0.3857987 0.1132121 -0.1102196 0.0000000 -0.0446466 -4.0329547 - - Initial C Matrix: - - 1 2 3 4 5 6 7 - - 1 -1.0015436 0.2336245 0.0000000 0.0856842 0.0000000 -0.0482226 -0.0000000 - 2 0.0071893 -1.0579388 -0.0000000 -0.3601105 -0.0000000 0.4631213 0.0000000 - 3 -0.0000000 -0.0000000 1.0610702 0.0000000 -0.0000000 -0.0000000 0.2965071 - 4 0.0002671 -0.4272843 -0.0000000 0.9399425 0.0000000 0.2129401 0.0000000 - 5 0.0000000 0.0000000 -0.0000000 0.0000000 -1.0000000 -0.0000000 -0.0000000 - 6 -0.0018213 0.1492533 -0.1377210 -0.0378579 0.0000000 -0.7807003 -0.8501403 - 7 -0.0018213 0.1492533 0.1377210 -0.0378579 -0.0000000 -0.7807003 0.8501403 - - Initial Density Matrix: - - 1 2 3 4 5 6 7 - - 1 1.0650117 -0.2852166 -0.0000000 -0.0195534 -0.0000000 0.0334496 0.0334496 - 2 -0.2852166 1.2489657 0.0000000 0.1135594 0.0000000 -0.1442809 -0.1442809 - 3 -0.0000000 0.0000000 1.1258701 -0.0000000 -0.0000000 -0.1461317 0.1461317 - 4 -0.0195534 0.1135594 -0.0000000 1.0660638 0.0000000 -0.0993583 -0.0993583 - 5 -0.0000000 0.0000000 -0.0000000 0.0000000 1.0000000 -0.0000000 -0.0000000 - 6 0.0334496 -0.1442809 -0.1461317 -0.0993583 -0.0000000 0.0426802 0.0047460 - 7 0.0334496 -0.1442809 0.1461317 -0.0993583 -0.0000000 0.0047460 0.0426802 - - - Iter E(elec) E(tot) Delta(E) RMS(D) - 00 -125.842077437699 -117.839710375888 - - Fock Matrix: - - 1 2 3 4 5 6 7 - - 1 -18.8132695 -4.8726875 -0.0000000 -0.0115290 0.0000000 -0.8067323 -0.8067323 - 2 -4.8726875 -1.7909029 -0.0000000 -0.1808692 0.0000000 -0.5790557 -0.5790557 - 3 -0.0000000 -0.0000000 0.1939644 0.0000000 0.0000000 -0.1708886 0.1708886 - 4 -0.0115290 -0.1808692 0.0000000 0.2391247 0.0000000 -0.1828683 -0.1828683 - 5 0.0000000 0.0000000 0.0000000 0.0000000 0.3091071 0.0000000 0.0000000 - 6 -0.8067323 -0.5790557 -0.1708886 -0.1828683 0.0000000 -0.1450338 -0.1846675 - 7 -0.8067323 -0.5790557 0.1708886 -0.1828683 0.0000000 -0.1846675 -0.1450338 - 01 -78.286583284740 -70.284216222929 47.555494152959 1.826673084479 - 02 -84.048316253435 -76.045949191625 -5.761732968696 0.479570364860 - 03 -82.716965960855 -74.714598899044 1.331350292581 0.086831688906 - 04 -82.987140757002 -74.984773695191 -0.270174796147 0.031026136359 - 05 -82.938133187513 -74.935766125703 0.049007569488 0.010799283179 - 06 -82.946271078699 -74.943904016889 -0.008137891186 0.005254826831 - 07 -82.944486784914 -74.942119723104 0.001784293785 0.002438579642 - 08 -82.944617252243 -74.942250190433 -0.000130467329 0.001177279531 - 09 -82.944503500703 -74.942136438892 0.000113751541 0.000564543180 - 10 -82.944478930626 -74.942111868815 0.000024570077 0.000272204992 - 11 -82.944461627684 -74.942094565874 0.000017302941 0.000131180309 - 12 -82.944454198375 -74.942087136564 0.000007429310 0.000063275666 - 13 -82.944450445051 -74.942083383241 0.000003753324 0.000030522547 - 14 -82.944448661686 -74.942081599875 0.000001783365 0.000014725847 - 15 -82.944447795931 -74.942080734120 0.000000865755 0.000007104836 - 16 -82.944447379016 -74.942080317206 0.000000416914 0.000003428026 - 17 -82.944447177685 -74.942080115875 0.000000201331 0.000001654014 - 18 -82.944447080565 -74.942080018755 0.000000097120 0.000000798065 - 19 -82.944447033699 -74.942079971888 0.000000046867 0.000000385069 - 20 -82.944447011086 -74.942079949276 0.000000022613 0.000000185798 - 21 -82.944447000175 -74.942079938365 0.000000010911 0.000000089648 - 22 -82.944446994911 -74.942079933100 0.000000005264 0.000000043256 - 23 -82.944446992371 -74.942079930560 0.000000002540 0.000000020871 - 24 -82.944446991145 -74.942079929334 0.000000001226 0.000000010070 - 25 -82.944446990554 -74.942079928743 0.000000000591 0.000000004859 - 26 -82.944446990268 -74.942079928458 0.000000000285 0.000000002345 - 27 -82.944446990130 -74.942079928320 0.000000000138 0.000000001131 - 28 -82.944446990064 -74.942079928254 0.000000000066 0.000000000546 - 29 -82.944446990032 -74.942079928222 0.000000000032 0.000000000263 - 30 -82.944446990016 -74.942079928206 0.000000000016 0.000000000127 - 31 -82.944446990009 -74.942079928199 0.000000000007 0.000000000061 - 32 -82.944446990005 -74.942079928195 0.000000000004 0.000000000030 - 33 -82.944446990004 -74.942079928193 0.000000000002 0.000000000014 - 34 -82.944446990003 -74.942079928192 0.000000000001 0.000000000007 - - 1 2 3 4 5 6 7 - - 1 -0.0000000 -0.0000000 -0.0507919 0.0000000 0.0000000 -0.0022297 0.0022297 - 2 -0.0000000 -0.0000000 -0.6411728 0.0000000 -0.0000000 -0.2627425 0.2627425 - 3 -0.0507919 -0.6411728 -0.0000000 0.0000000 -0.0000000 -0.4376306 -0.4376306 - 4 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.1473994 0.1473994 - 5 0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 - 6 -0.0022297 -0.2627425 -0.4376306 -0.1473994 0.0000000 -1.6380368 0.0000000 - 7 0.0022297 0.2627425 -0.4376306 0.1473994 -0.0000000 0.0000000 1.6380368 - - 1 2 3 4 5 6 7 - - 1 1.0548737 -0.2327977 -0.0000000 0.0526229 -0.0000000 -0.0081506 -0.0081506 - 2 -0.2327977 1.0151108 0.0000000 -0.2823000 0.0000000 -0.0305395 -0.0305395 - 3 -0.0000000 0.0000000 0.3687949 -0.0000000 -0.0000000 0.2750987 -0.2750987 - 4 0.0526229 -0.2823000 -0.0000000 0.5660419 0.0000000 0.2586150 0.2586150 - 5 -0.0000000 0.0000000 -0.0000000 0.0000000 1.0000000 -0.0000000 -0.0000000 - 6 -0.0081506 -0.0305395 0.2750987 0.2586150 -0.0000000 0.3345267 -0.0758872 - 7 -0.0081506 -0.0305395 -0.2750987 0.2586150 -0.0000000 -0.0758872 0.3345267 - -Mu-X = 0.000000000000 -Mu-Y = 0.603521296525 -Mu-Z = -0.000000000000 -Total dipole moment (au) = 0.603521296525 - -Charge on atom 0: -0.253146052405 -Charge on atom 1: 0.126573026202 -Charge on atom 2: 0.126573026202 diff --git a/Project#03/project3-instructions.pdf b/Project#03/project3-instructions.pdf deleted file mode 100644 index ee6cc415282a47f446450e3c0223c24fca97277a..0000000000000000000000000000000000000000 GIT binary patch literal 0 HcmV?d00001 literal 92791 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Nevertheless, you should start with this algorithm to get your code working, and run timings (use the UNIX "time" command) for the test cases below to get an idea of its computational cost. - - * [Hint 1](./hints/hint1.md): Noddy transformation code -### The Smarter Algorithm - -Notice that none of the *C* coefficients in the above expression have any indices in common. Thus, the summation could be rearranged such that: - - - -This means that each summation within brackets could be carried out separately, -starting from the innermost summation over σ, if we store the results at each step. This reduces the N8 algorithm above to four N5 steps. - -Be careful about the permutational symmetry of the integrals and intermediates at each step: -while the AO-basis integrals have eight-fold permutational symmetry, the partially transformed integrals have much less symmetry. - -After you have the noddy algorithm working and timed, modify it to use this smarter algorithm and time the test cases again. Enjoy! - - * [Hint 2](./hints/hint2.md): Smarter transformation code - -## Step #4: Compute the MP2 Energy - - - -where *i* and *j* denote doubly-occupied orbitals and *a* and *b* unoccupied orbitals, and the denominator involves the MO energies. - - * [Hint 3](./hints/hint3.md): Occupied versus unoccupied orbitals - -## Test Cases -The input structures, integrals, etc. for these examples are found in the [input directory](./input). - -* STO-3G Water | [output](./output/h2o/STO-3G/output.txt) -* DZ Water | [output](./output/h2o/DZ/output.txt) -* DZP Water | [output](./output/h2o/DZP/output.txt) -* STO-3G Methane | [output](./output/ch4/STO-3G/output.txt) - diff --git a/Project#04/figures/eri.png b/Project#04/figures/eri.png deleted file mode 100644 index b1d8f525abb164771229486952e0851b72061ecc..0000000000000000000000000000000000000000 GIT binary patch literal 0 HcmV?d00001 literal 24786 zcmagF2UL?w*ES4@4W-yXIw**W^xma+LhnUNfRKa`(&&gNs7O!{kS-w7gY;gM5&;3J 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a/Project#04/hints/hint1.md +++ /dev/null @@ -1,37 +0,0 @@ -Here's a code block that demonstrates how to carry out the AO to MO two-electron integral transformation using a single N8 step. Note that the original AO- and transformed MO-basis integrals are stored in a one-dimensional array taking full advantage of their eight-fold permutational symmetry, as described in [Project #3](../../Project%2303). - -Note how the loop structure in the MO-indices (*i*, *j*, *k*, and *l*) automatically takes into account the permutational symmetry of the fully transformed integrals. - -```c++ - #define INDEX(i,j) ((i>j) ? (((i)*((i)+1)/2)+(j)) : (((j)*((j)+1)/2)+(i))) - ... - double *TEI_AO, *TEI_MO; - int i, j, k, l, ijkl; - int p, q, r, s, pq, rs, pqrs; - ... - - for(i=0,ijkl=0; i < nao; i++) { - for(j=0; j <= i; j++) { - for(k=0; k <= i; k++) { - for(l=0; l <= (i==k ? j : k); l++,ijkl++) { - - for(p=0; p < nao; p++) { - for(q=0; q < nao; q++) { - pq = INDEX(p,q); - for(r=0; r < nao; r++) { - for(s=0; s < nao; s++) { - rs = INDEX(r,s); - pqrs = INDEX(pq,rs); - - TEI_MO[ijkl] += C[p][i] * C[q][j] * C[r][k] * C[s][l] * TEI_AO[pqrs]; - - } - } - } - } - - } - } - } - } -``` diff --git a/Project#04/hints/hint2.md b/Project#04/hints/hint2.md deleted file mode 100644 index 79a46dd..0000000 --- a/Project#04/hints/hint2.md +++ /dev/null @@ -1,59 +0,0 @@ -Here's a code block that demonstrates how to carry out the AO to MO two-electron integral transformation using four N5 steps. Note that the original AO- and transformed MO-basis integrals are stored in a one-dimensional array taking advantage of their eight-fold permutational symmetry, as described in [Project #3](../../Project%2303). However, the half-transformed integrals, which lack bra-ket permutational symmetry, are stored in a two-dimensional array. - -A number of convenient functions [`mmult()`, `init_matrix()`, etc.] used in this code block can be found in the [diag.cc](http://sirius.chem.vt.edu/~crawdad/programming/diag.cc) discussed in [Project #1](../../Project%2301). - -```c++ - #define INDEX(i,j) ((i>j) ? (((i)*((i)+1)/2)+(j)) : (((j)*((j)+1)/2)+(i))) - ... - double **X, **Y, **TMP, *TEI; - int i, j, k, l, ij, kl, ijkl, klij; - - ... - X = init_matrix(nao, nao); - Y = init_matrix(nao, nao); - - TMP = init_matrix((nao*(nao+1)/2),(nao*(nao+1)/2)); - for(i=0,ij=0; i < nao; i++) - for(j=0; j <= i; j++,ij++) { - for(k=0,kl=0; k < nao; k++) - for(l=0; l <= k; l++,kl++) { - ijkl = INDEX(ij,kl); - X[k][l] = X[l][k] = TEI[ijkl]; - } - zero_matrix(Y, nao, nao); - mmult(C, 1, X, 0, Y, nao, nao, nao); - zero_matrix(X, nao, nao); - mmult(Y, 0, C, 0, X, nao, nao, nao); - for(k=0, kl=0; k < nao; k++) - for(l=0; l <= k; l++, kl++) - TMP[kl][ij] = X[k][l]; - } - - zero_array(TEI, (nao*(nao+1)/2)*((nao*(nao+1)/2)+1)/2); - - for(k=0,kl=0; k < nao; k++) - for(l=0; l <= k; l++,kl++) { - zero_matrix(X, nao, nao); - zero_matrix(Y, nao, nao); - for(i=0,ij=0; i < nao; i++) - for(j=0; j <=i; j++,ij++) - X[i][j] = X[j][i] = TMP[kl][ij]; - zero_matrix(Y, nao, nao); - mmult(C, 1, X, 0, Y, nao, nao, nao); - zero_matrix(X, nao, nao); - mmult(Y, 0, C, 0, X, nao, nao, nao); - for(i=0, ij=0; i < nao; i++) - for(j=0; j <= i; j++,ij++) { - klij = INDEX(kl,ij); - TEI[klij] = X[i][j]; - } - } - - ... - - free_matrix(X, nao); - free_matrix(Y, nao); - free_matrix(TMP, (nao*(nao+1)/2)); - -``` - diff --git a/Project#04/hints/hint3.md b/Project#04/hints/hint3.md deleted file mode 100644 index d6ae3ab..0000000 --- a/Project#04/hints/hint3.md +++ /dev/null @@ -1,20 +0,0 @@ -The following code block illustrates a simple-minded MP2 energy calculation with the two-electron integrals stored in a one-dimensional array. The molecular orbitals are assumed to be ordered with all doubly-occupied orbitals first, followed by the unoccupied/virtual orbitals. Notice the difference in limits of the loops over *i* and *a*: - -```c++ - Emp2 = 0.0; - for(i=0; i < ndocc; i++) { - for(a=ndocc; a < nao; a++) { - ia = INDEX(i,a); - for(j=0; j < ndocc; j++) { - ja = INDEX(j,a); - for(b=ndocc; b < nao; b++) { - jb = INDEX(j,b); - ib = INDEX(i,b); - iajb = INDEX(ia,jb); - ibja = INDEX(ib,ja); - Emp2 += TEI[iajb] * (2 * TEI[iajb] - TEI[ibja])/(eps[i] + eps[j] - eps[a] - eps[b]); - } - } - } - } -``` diff --git a/Project#04/input/ch4/STO-3G/enuc.dat b/Project#04/input/ch4/STO-3G/enuc.dat deleted file mode 100644 index feb8199..0000000 --- a/Project#04/input/ch4/STO-3G/enuc.dat +++ /dev/null @@ -1 +0,0 @@ - 13.497304462036480 diff --git a/Project#04/input/ch4/STO-3G/eri.dat b/Project#04/input/ch4/STO-3G/eri.dat deleted file mode 100644 index b1c1a16..0000000 --- a/Project#04/input/ch4/STO-3G/eri.dat +++ /dev/null @@ -1,912 +0,0 @@ - 1 1 1 1 3.541948297688456 - 2 1 1 1 0.576921328341946 - 2 2 1 1 0.854681772892244 - 2 1 2 1 0.111888125975301 - 2 2 2 1 0.205283870818581 - 2 2 2 2 0.624708798510611 - 3 3 1 1 0.852436095451127 - 4 4 1 1 0.852436095451127 - 5 5 1 1 0.852436095451127 - 3 1 3 1 0.020296465970775 - 4 1 4 1 0.020296465970775 - 5 1 5 1 0.020296465970775 - 3 3 2 1 0.205335088917950 - 4 4 2 1 0.205335088917950 - 5 5 2 1 0.205335088917950 - 3 2 3 1 0.030857749607787 - 4 2 4 1 0.030857749607787 - 5 2 5 1 0.030857749607787 - 3 3 2 2 0.624568373997849 - 4 4 2 2 0.624568373997849 - 5 5 2 2 0.624568373997849 - 3 2 3 2 0.137996275062609 - 4 2 4 2 0.137996275062609 - 5 2 5 2 0.137996275062609 - 3 3 3 3 0.672832726154768 - 4 3 4 3 0.036268641177034 - 4 4 3 3 0.600295443800700 - 4 4 4 4 0.672832726154768 - 5 3 5 3 0.036268641177034 - 5 4 5 4 0.036268641177034 - 5 5 3 3 0.600295443800700 - 5 5 4 4 0.600295443800700 - 5 5 5 5 0.672832726154768 - 6 1 1 1 0.147608605517858 - 6 2 1 1 0.335162193482858 - 6 1 2 1 0.028436223207717 - 6 2 2 1 0.081484132039537 - 6 1 2 2 0.052013862829475 - 6 2 2 2 0.270610027447356 - 6 3 1 1 0.160685542140597 - 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9c536a9..0000000 --- a/Project#04/input/ch4/STO-3G/geom.dat +++ /dev/null @@ -1,6 +0,0 @@ -5 -6.000000000000 -0.000000000000 0.000000000000 0.000000000000 -1.000000000000 1.183771681898 -1.183771681898 -1.183771681898 -1.000000000000 1.183771681898 1.183771681898 1.183771681898 -1.000000000000 -1.183771681898 1.183771681898 -1.183771681898 -1.000000000000 -1.183771681898 -1.183771681898 1.183771681898 diff --git a/Project#04/input/ch4/STO-3G/input.dat b/Project#04/input/ch4/STO-3G/input.dat deleted file mode 100644 index 6dfb483..0000000 --- a/Project#04/input/ch4/STO-3G/input.dat +++ /dev/null @@ -1,43 +0,0 @@ -psi: ( - label = "CH4 SCF Test Case" - wfn = scf - jobtype = oeprop - reference = rhf - basis = "STO-3G" - units = angstrom - subgroup = c1 - delete_tei = false - delete_oei = false - zmat = ( - C - H 1 r - H 1 r 2 td - H 1 r 2 td 3 d - H 1 r 2 td 4 d - ) - zvars = ( - r 1.085 - td 109.47122063449069136958 - d 120.0 - ) -) - -basis: ( - carbon: "STO-3G" = - ( (S ( 71.61683730 0.15432900) - ( 13.04509630 0.53532810) - ( 3.53051220 0.44463450) ) - (S ( 2.94124940 -0.09996720) - ( 0.68348310 0.39951280) - ( 0.22228990 0.70011550) ) - (P ( 2.94124940 0.15591630) - ( 0.68348310 0.60768370) - ( 0.22228990 0.39195740) ) - ) - - hydrogen: "STO-3G"= - ( (S ( 3.42525090 0.15432890) - ( 0.62391370 0.53532810) - ( 0.16885540 0.44463450) ) - ) -) diff --git a/Project#04/input/ch4/STO-3G/mux.dat b/Project#04/input/ch4/STO-3G/mux.dat deleted file mode 100644 index 9dca8dd..0000000 --- a/Project#04/input/ch4/STO-3G/mux.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 0.000000000000000 - 2 1 0.000000000000000 - 2 2 0.000000000000000 - 3 1 -0.071855488532817 - 3 2 -0.838743574800986 - 3 3 0.000000000000000 - 4 1 -0.000000000000000 - 4 2 0.000000000000000 - 4 3 -0.000000000000000 - 4 4 0.000000000000000 - 5 1 0.000000000000000 - 5 2 0.000000000000000 - 5 3 -0.000000000000000 - 5 4 0.000000000000000 - 5 5 0.000000000000000 - 6 1 -0.004780775261548 - 6 2 -0.306592476518555 - 6 3 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diff --git a/Project#04/input/h2o/DZP/input.dat b/Project#04/input/h2o/DZP/input.dat deleted file mode 100644 index 8cf45b4..0000000 --- a/Project#04/input/h2o/DZP/input.dat +++ /dev/null @@ -1,13 +0,0 @@ -psi: ( - label = "H2O SCF Test Case" - memory = (10.0 MB) - wfn = scf - jobtype = oeprop - delete_tei = false - delete_oei = false - reference = rhf - puream = false - basis = "DZP" - subgroup = c1 - zmat = ((o) (h 1 1.1) (h 1 1.1 2 104.0)) -) diff --git a/Project#04/input/h2o/DZP/mux.dat b/Project#04/input/h2o/DZP/mux.dat deleted file mode 100644 index 9eeb14c..0000000 --- a/Project#04/input/h2o/DZP/mux.dat +++ /dev/null @@ -1,351 +0,0 @@ - 1 1 -0.000000000000000 - 2 1 -0.000000000000000 - 2 2 -0.000000000000000 - 3 1 -0.000000000000000 - 3 2 -0.000000000000000 - 3 3 -0.000000000000000 - 4 1 -0.000000000000000 - 4 2 -0.000000000000000 - 4 3 -0.000000000000000 - 4 4 -0.000000000000000 - 5 1 -0.065756994029223 - 5 2 -0.076390812514647 - 5 3 -0.495548317796719 - 5 4 -0.578524588047388 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0.235420950941441 - 7 7 7 3 -0.206690042488560 - 7 7 7 4 0.161483959338374 - 7 7 7 6 0.091353706761488 - 7 7 7 7 0.774605943919898 diff --git a/Project#04/input/h2o/STO-3G/geom.dat b/Project#04/input/h2o/STO-3G/geom.dat deleted file mode 100644 index 99b165d..0000000 --- a/Project#04/input/h2o/STO-3G/geom.dat +++ /dev/null @@ -1,4 +0,0 @@ -3 -8.000000000000 0.000000000000 -0.143225816552 0.000000000000 -1.000000000000 1.638036840407 1.136548822547 -0.000000000000 -1.000000000000 -1.638036840407 1.136548822547 -0.000000000000 diff --git a/Project#04/input/h2o/STO-3G/input.dat b/Project#04/input/h2o/STO-3G/input.dat deleted file mode 100644 index f8c5067..0000000 --- a/Project#04/input/h2o/STO-3G/input.dat +++ /dev/null @@ -1,12 +0,0 @@ -psi: ( - label = "H2O SCF Test Case" - memory = (10.0 MB) - wfn = scf - jobtype = oeprop - delete_tei = false - delete_oei = false - reference = rhf - basis = "STO-3G" - subgroup = c1 - zmat = ((o) (h 1 1.1) (h 1 1.1 2 104.0)) -) diff --git a/Project#04/input/h2o/STO-3G/mux.dat b/Project#04/input/h2o/STO-3G/mux.dat deleted file mode 100644 index c5d92c5..0000000 --- a/Project#04/input/h2o/STO-3G/mux.dat +++ /dev/null @@ -1,28 +0,0 @@ - 1 1 -0.000000000000000 - 2 1 -0.000000000000000 - 2 2 -0.000000000000000 - 3 1 -0.050791929587912 - 3 2 -0.641172844324925 - 3 3 -0.000000000000000 - 4 1 0.000000000000000 - 4 2 0.000000000000000 - 4 3 0.000000000000000 - 4 4 -0.000000000000000 - 5 1 0.000000000000000 - 5 2 -0.000000000000000 - 5 3 -0.000000000000000 - 5 4 0.000000000000000 - 5 5 -0.000000000000000 - 6 1 -0.002229654052248 - 6 2 -0.262742503532769 - 6 3 -0.437630646182039 - 6 4 -0.147399448800486 - 6 5 0.000000000000000 - 6 6 -1.638036840407314 - 7 1 0.002229654052248 - 7 2 0.262742503532769 - 7 3 -0.437630646182039 - 7 4 0.147399448800486 - 7 5 -0.000000000000000 - 7 6 0.000000000000000 - 7 7 1.638036840407314 diff --git a/Project#04/input/h2o/STO-3G/muy.dat b/Project#04/input/h2o/STO-3G/muy.dat deleted file mode 100644 index 1efcbad..0000000 --- a/Project#04/input/h2o/STO-3G/muy.dat +++ /dev/null @@ -1,28 +0,0 @@ - 1 1 0.143225816551918 - 2 1 0.033902114587819 - 2 2 0.143225816551918 - 3 1 -0.000000000000000 - 3 2 0.000000000000000 - 3 3 0.143225816551918 - 4 1 -0.050791929587912 - 4 2 -0.641172844324925 - 4 3 -0.000000000000000 - 4 4 0.143225816551918 - 5 1 -0.000000000000000 - 5 2 0.000000000000000 - 5 3 0.000000000000000 - 5 4 -0.000000000000000 - 5 5 0.143225816551918 - 6 1 0.003758676726377 - 6 2 -0.149971890752635 - 6 3 -0.108952162150434 - 6 4 -0.334090713364948 - 6 5 0.000000000000000 - 6 6 -1.136548822546795 - 7 1 0.003758676726377 - 7 2 -0.149971890752635 - 7 3 0.108952162150434 - 7 4 -0.334090713364948 - 7 5 0.000000000000000 - 7 6 -0.206578984758302 - 7 7 -1.136548822546794 diff --git a/Project#04/input/h2o/STO-3G/muz.dat b/Project#04/input/h2o/STO-3G/muz.dat deleted file mode 100644 index 35dfd9f..0000000 --- a/Project#04/input/h2o/STO-3G/muz.dat +++ /dev/null @@ -1,28 +0,0 @@ - 1 1 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0.000000000000000 - 3 3 1.000000000000000 - 4 1 -0.000000000000000 - 4 2 -0.000000000000000 - 4 3 -0.000000000000000 - 4 4 1.000000000000000 - 5 1 -0.000000000000000 - 5 2 0.000000000000000 - 5 3 0.000000000000000 - 5 4 -0.000000000000000 - 5 5 1.000000000000000 - 6 1 0.038405599785757 - 6 2 0.386138840478249 - 6 3 0.268438243716457 - 6 4 0.209726941420375 - 6 5 -0.000000000000000 - 6 6 1.000000000000000 - 7 1 0.038405599785757 - 7 2 0.386138840478250 - 7 3 -0.268438243716457 - 7 4 0.209726941420375 - 7 5 -0.000000000000000 - 7 6 0.181759886298063 - 7 7 1.000000000000000 diff --git a/Project#04/input/h2o/STO-3G/t.dat b/Project#04/input/h2o/STO-3G/t.dat deleted file mode 100644 index 8927c33..0000000 --- a/Project#04/input/h2o/STO-3G/t.dat +++ /dev/null @@ -1,28 +0,0 @@ - 1 1 29.003199945539588 - 2 1 -0.168010939316492 - 2 2 0.808127954930347 - 3 1 0.000000000000000 - 3 2 0.000000000000000 - 3 3 2.528731198194763 - 4 1 0.000000000000000 - 4 2 -0.000000000000000 - 4 3 -0.000000000000000 - 4 4 2.528731198194763 - 5 1 -0.000000000000000 - 5 2 0.000000000000000 - 5 3 0.000000000000000 - 5 4 -0.000000000000000 - 5 5 2.528731198194763 - 6 1 -0.008416383544591 - 6 2 0.070517372751001 - 6 3 0.147090913304052 - 6 4 0.114920016354202 - 6 5 -0.000000000000000 - 6 6 0.760031883566609 - 7 1 -0.008416383544591 - 7 2 0.070517372751002 - 7 3 -0.147090913304052 - 7 4 0.114920016354202 - 7 5 -0.000000000000000 - 7 6 -0.003979868621841 - 7 7 0.760031883566609 diff --git a/Project#04/input/h2o/STO-3G/v.dat b/Project#04/input/h2o/STO-3G/v.dat deleted file mode 100644 index d5b7411..0000000 --- a/Project#04/input/h2o/STO-3G/v.dat +++ /dev/null @@ -1,28 +0,0 @@ - 1 1 -61.580595358149914 - 2 1 -7.410821877330996 - 2 2 -10.009071226859687 - 3 1 0.000000000000000 - 3 2 0.000000000000000 - 3 3 -9.987550507419133 - 4 1 -0.014473835903318 - 4 2 -0.176890246723779 - 4 3 0.000000000000000 - 4 4 -9.944042952440439 - 5 1 0.000000000000000 - 5 2 0.000000000000000 - 5 3 -0.000000000000000 - 5 4 0.000000000000000 - 5 5 -9.875876065926128 - 6 1 -1.231685872788711 - 6 2 -2.977227202971528 - 6 3 -1.822241058022723 - 6 4 -1.471788274313766 - 6 5 0.000000000000000 - 6 6 -5.300202953839792 - 7 1 -1.231685872788712 - 7 2 -2.977227202971529 - 7 3 1.822241058022724 - 7 4 -1.471788274313766 - 7 5 0.000000000000001 - 7 6 -1.067166014696110 - 7 7 -5.300202953839793 diff --git a/Project#04/output/ch4/STO-3G/output.txt b/Project#04/output/ch4/STO-3G/output.txt deleted file mode 100644 index 50d24d1..0000000 --- a/Project#04/output/ch4/STO-3G/output.txt +++ /dev/null @@ -1,3 +0,0 @@ -Escf = -39.726850324347 -Emp2 = -0.056046676165 -Etot = -39.782897000512 diff --git a/Project#04/output/h2o/DZ/output.txt b/Project#04/output/h2o/DZ/output.txt deleted file mode 100644 index caa92c7..0000000 --- a/Project#04/output/h2o/DZ/output.txt +++ /dev/null @@ -1,3 +0,0 @@ -Escf = -75.977878975377 -Emp2 = -0.152709879075 -Etot = -76.130588854452 diff --git a/Project#04/output/h2o/DZP/output.txt b/Project#04/output/h2o/DZP/output.txt deleted file mode 100644 index d3e27b9..0000000 --- a/Project#04/output/h2o/DZP/output.txt +++ /dev/null @@ -1,3 +0,0 @@ -Escf = -76.008821792901 -Emp2 = -0.222519233815 -Etot = -76.231341026716 diff --git a/Project#04/output/h2o/STO-3G/output.txt b/Project#04/output/h2o/STO-3G/output.txt deleted file mode 100644 index 28f6056..0000000 --- a/Project#04/output/h2o/STO-3G/output.txt +++ /dev/null @@ -1,3 +0,0 @@ -Escf = -74.942079928192 -Emp2 = -0.049149636120 -Etot = -74.991229564312 diff --git a/Project#04/project4-instructions.pdf b/Project#04/project4-instructions.pdf deleted file mode 100644 index 6a8da0b9b3b6cb4f473510db1516c091521ba55c..0000000000000000000000000000000000000000 GIT binary patch literal 0 HcmV?d00001 literal 72790 zcmd?QbzGIt_Am;Fq)15Trn@%X-QCjC9nv8oNOwqwq;#otryz}jba%J(-5bHL=l7oT zzUSWi&;5L^eCC;X)~s2xX4R}c&q%H)Do)SLz=}XV{JrZZ0t_|a%CggkRgNj7Wcbj zu8)k=)AeX6m_s7eIV2ZlNts^H8-N2`ADgEkEgxHfI>1hp^Q9hP%{9Mbw7J4tY!^?O 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The purpose of this project is to understand the fundamental aspects of the calculation of the CCSD wave function and corresponding energy. A good reference article (with correct, factored equations!) is [J.F. Stanton, J. Gauss, J.D. Watts, and R.J. Bartlett, J. Chem. Phys. volume 94, pp. 4334-4345 (1991)]( http://sirius.chem.vt.edu/wiki/lib/exe/fetch.php?media=crawdad:programming:jcp_94_4334_1991.pdf). -## Step #1: Preparing the Spin-Orbital Basis Integrals -Each term in the equations given in the above paper by Stanton et al. depends on the T1 or T2 -amplitudes as well as Fock-matrix elements and antisymmetrized, Dirac-notation two-electron integrals, all given in the molecular spin-orbital basis -(as opposed to the spatial-orbital basis used in the earlier [MP2 Project](../Project%2304). -Thus, the transformation of the AO-basis integrals into the spatial-MO basis must also include their translation into the spin-orbital basis: - - - -Thus, if you know the ordering of the orbitals (e.g. all occupied orbitals before virtual orbitals, perhaps alternating between alpha and beta spins), it is straightforward to carry out the integration over the spin components (the σ's) in the above expression. Thus, each spatial-orbital MO-basis two-electron integral translates to 16 possible spin-orbital integrals, only four of which are non-zero. - -Don't forget that you must also create the spin-orbital Fock matrix: - - - -Suggestion: For simplicity, store the two-electron integrals in a four-dimensional array. This will greatly facilitate debugging of the complicated CCSD equations. - - * [Hint 1](./hints/hint1.md): Sample spatial- to spin-orbital translation code. - -## Step #2: Build the Initial-Guess Cluster Amplitudes -For Hartree-Fock reference determinants, the most common initial guess for the cluster amplitudes are the Moller-Plesset first-order perturbed wave function: - - - -Note that if you have constructed the Fock matrix, two-electron integrals, and initial-guess amplitudes correctly at this point, -you should be able to compute the MP2 correlation energy using the simple spin-orbital expression and get identical results to those from [Project #4](../Project%2304): - - - -## Step #3: Calculate the CC Intermediates -Use the spin-orbital Eqs. 3-13 from Stanton's paper to build the two-index (F) and four-index (W) intermediates, as well as the effective doubles (labelled with the Greek letter τ). - -## Step #4: Compute the Updated Cluster Amplitudes -Use Eqs. 1 and 2 from Stanton's paper to compute the updated T1 and T2 cluster amplitudes. - -## Step #5: Check for Convergence and Iterate -Calculate the current CC correlation energy: - - - -Compare energies and cluster amplitudes (using RMS differences) between iterations to check for convergence to some specified cutoff. -If convergence is reached, you're done; if not, return to Step #3 and continue. - -## Test Cases -The input structures, integrals, etc. for these examples are found in the -[input directory](./input). - -* STO-3G Water | [output](./output/h2o/STO-3G/output.txt) -* DZ Water | [output](./output/h2o/DZ/output.txt) -* DZP Water | [output](./output/h2o/DZP/output.txt) -* STO-3G Methane | [output](./output/ch4/STO-3G/output.txt) diff --git a/Project#05/figures/cc-correlation-energy.png b/Project#05/figures/cc-correlation-energy.png deleted file mode 100644 index 0be10b24b98b8ae411a31fea697a0d44f25a8c36..0000000000000000000000000000000000000000 GIT binary patch literal 0 HcmV?d00001 literal 13855 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takes the one-dimensional array of MO-basis spatial-orbital two-electron integrals we've been using thus far and translates it to a four-dimensional array of antisymmetrized integrals over spin-orbitals. Note that alpha and beta spin functions alternate here, with even-numbered orbitals corresponding to alpha, and odd-numbered to beta. The variable `nmo` is the number of spin orbitals, and the `INDEX` function is the same as that [used before](../../Project%2303/hints/hint7-2.md). - -```c++ - /* Translate integrals to spin-orbital basis */ - for(p=0; p < nmo; p++) - for(q=0; q < nmo; q++) - for(r=0; r < nmo; r++) - for(s=0; s < nmo; s++) { - pr = INDEX(p/2,r/2); - qs = INDEX(q/2,s/2); - prqs = INDEX(pr,qs); - value1 = TEI[prqs] * (p%2 == r%2) * (q%2 == s%2); - ps = INDEX(p/2,s/2); - qr = INDEX(q/2,r/2); - psqr = INDEX(ps,qr); - value2 = TEI[psqr] * (p%2 == s%2) * (q%2 == r%2); - ints[p][q][r][s] = value1 - value2; - } -``` diff --git a/Project#05/input/ch4/STO-3G/enuc.dat b/Project#05/input/ch4/STO-3G/enuc.dat deleted file mode 100644 index feb8199..0000000 --- a/Project#05/input/ch4/STO-3G/enuc.dat +++ /dev/null @@ -1 +0,0 @@ - 13.497304462036480 diff --git a/Project#05/input/ch4/STO-3G/eri.dat b/Project#05/input/ch4/STO-3G/eri.dat deleted file mode 100644 index b1c1a16..0000000 --- a/Project#05/input/ch4/STO-3G/eri.dat +++ /dev/null @@ -1,912 +0,0 @@ - 1 1 1 1 3.541948297688456 - 2 1 1 1 0.576921328341946 - 2 2 1 1 0.854681772892244 - 2 1 2 1 0.111888125975301 - 2 2 2 1 0.205283870818581 - 2 2 2 2 0.624708798510611 - 3 3 1 1 0.852436095451127 - 4 4 1 1 0.852436095451127 - 5 5 1 1 0.852436095451127 - 3 1 3 1 0.020296465970775 - 4 1 4 1 0.020296465970775 - 5 1 5 1 0.020296465970775 - 3 3 2 1 0.205335088917950 - 4 4 2 1 0.205335088917950 - 5 5 2 1 0.205335088917950 - 3 2 3 1 0.030857749607787 - 4 2 4 1 0.030857749607787 - 5 2 5 1 0.030857749607787 - 3 3 2 2 0.624568373997849 - 4 4 2 2 0.624568373997849 - 5 5 2 2 0.624568373997849 - 3 2 3 2 0.137996275062609 - 4 2 4 2 0.137996275062609 - 5 2 5 2 0.137996275062609 - 3 3 3 3 0.672832726154768 - 4 3 4 3 0.036268641177034 - 4 4 3 3 0.600295443800700 - 4 4 4 4 0.672832726154768 - 5 3 5 3 0.036268641177034 - 5 4 5 4 0.036268641177034 - 5 5 3 3 0.600295443800700 - 5 5 4 4 0.600295443800700 - 5 5 5 5 0.672832726154768 - 6 1 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0.085276746780538 - 9 9 9 9 0.774605895725855 diff --git a/Project#05/input/ch4/STO-3G/geom.dat b/Project#05/input/ch4/STO-3G/geom.dat deleted file mode 100644 index 9c536a9..0000000 --- a/Project#05/input/ch4/STO-3G/geom.dat +++ /dev/null @@ -1,6 +0,0 @@ -5 -6.000000000000 -0.000000000000 0.000000000000 0.000000000000 -1.000000000000 1.183771681898 -1.183771681898 -1.183771681898 -1.000000000000 1.183771681898 1.183771681898 1.183771681898 -1.000000000000 -1.183771681898 1.183771681898 -1.183771681898 -1.000000000000 -1.183771681898 -1.183771681898 1.183771681898 diff --git a/Project#05/input/ch4/STO-3G/input.dat b/Project#05/input/ch4/STO-3G/input.dat deleted file mode 100644 index 6dfb483..0000000 --- a/Project#05/input/ch4/STO-3G/input.dat +++ /dev/null @@ -1,43 +0,0 @@ -psi: ( - label = "CH4 SCF Test Case" - wfn = scf - jobtype = oeprop - reference = rhf - basis = "STO-3G" - units = angstrom - subgroup = c1 - delete_tei = false - delete_oei = false - zmat = ( - C - H 1 r - H 1 r 2 td - H 1 r 2 td 3 d - H 1 r 2 td 4 d - ) - zvars = ( - r 1.085 - td 109.47122063449069136958 - d 120.0 - ) -) - -basis: ( - carbon: "STO-3G" = - ( (S ( 71.61683730 0.15432900) - ( 13.04509630 0.53532810) - ( 3.53051220 0.44463450) ) - (S ( 2.94124940 -0.09996720) - ( 0.68348310 0.39951280) - ( 0.22228990 0.70011550) ) - (P ( 2.94124940 0.15591630) - ( 0.68348310 0.60768370) - ( 0.22228990 0.39195740) ) - ) - - hydrogen: "STO-3G"= - ( (S ( 3.42525090 0.15432890) - ( 0.62391370 0.53532810) - ( 0.16885540 0.44463450) ) - ) -) diff --git a/Project#05/input/ch4/STO-3G/mux.dat b/Project#05/input/ch4/STO-3G/mux.dat deleted file mode 100644 index 9dca8dd..0000000 --- a/Project#05/input/ch4/STO-3G/mux.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 0.000000000000000 - 2 1 0.000000000000000 - 2 2 0.000000000000000 - 3 1 -0.071855488532817 - 3 2 -0.838743574800986 - 3 3 0.000000000000000 - 4 1 -0.000000000000000 - 4 2 0.000000000000000 - 4 3 -0.000000000000000 - 4 4 0.000000000000000 - 5 1 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a/Project#05/input/ch4/STO-3G/muy.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 -0.000000000000000 - 2 1 -0.000000000000000 - 2 2 -0.000000000000000 - 3 1 -0.000000000000000 - 3 2 0.000000000000000 - 3 3 -0.000000000000000 - 4 1 -0.071855488532817 - 4 2 -0.838743574800986 - 4 3 0.000000000000000 - 4 4 -0.000000000000000 - 5 1 -0.000000000000000 - 5 2 -0.000000000000000 - 5 3 0.000000000000000 - 5 4 -0.000000000000000 - 5 5 -0.000000000000000 - 6 1 0.004780775261548 - 6 2 0.306592476518555 - 6 3 0.163831354490276 - 6 4 -0.519567036508228 - 6 5 -0.163831354490276 - 6 6 1.183771681897730 - 7 1 -0.004780775261548 - 7 2 -0.306592476518555 - 7 3 -0.163831354490276 - 7 4 -0.519567036508228 - 7 5 -0.163831354490276 - 7 6 -0.000000000000000 - 7 7 -1.183771681897730 - 8 1 -0.004780775261548 - 8 2 -0.306592476518555 - 8 3 0.163831354490276 - 8 4 -0.519567036508228 - 8 5 0.163831354490276 - 8 6 -0.000000000000000 - 8 7 -0.202918556316052 - 8 8 -1.183771681897730 - 9 1 0.004780775261548 - 9 2 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a/Project#05/input/h2o/DZ/geom.dat +++ /dev/null @@ -1,4 +0,0 @@ -3 -8.000000000000 0.000000000000 -0.143225816552 0.000000000000 -1.000000000000 1.638036840407 1.136548822547 -0.000000000000 -1.000000000000 -1.638036840407 1.136548822547 -0.000000000000 diff --git a/Project#05/input/h2o/DZ/input.dat b/Project#05/input/h2o/DZ/input.dat deleted file mode 100644 index c9eeb62..0000000 --- a/Project#05/input/h2o/DZ/input.dat +++ /dev/null @@ -1,12 +0,0 @@ -psi: ( - label = "H2O SCF Test Case" - memory = (10.0 MB) - wfn = scf - jobtype = oeprop - delete_tei = false - delete_oei = false - reference = rhf - basis = "DZ" - subgroup = c1 - zmat = ((o) (h 1 1.1) (h 1 1.1 2 104.0)) -) diff --git a/Project#05/input/h2o/DZ/mux.dat b/Project#05/input/h2o/DZ/mux.dat deleted file mode 100644 index 900a852..0000000 --- a/Project#05/input/h2o/DZ/mux.dat +++ /dev/null @@ -1,105 +0,0 @@ - 1 1 -0.000000000000000 - 2 1 -0.000000000000000 - 2 2 -0.000000000000000 - 3 1 -0.000000000000000 - 3 2 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0.161483959338374 - 7 7 7 6 0.091353706761488 - 7 7 7 7 0.774605943919898 diff --git a/Project#05/input/h2o/STO-3G/geom.dat b/Project#05/input/h2o/STO-3G/geom.dat deleted file mode 100644 index 99b165d..0000000 --- a/Project#05/input/h2o/STO-3G/geom.dat +++ /dev/null @@ -1,4 +0,0 @@ -3 -8.000000000000 0.000000000000 -0.143225816552 0.000000000000 -1.000000000000 1.638036840407 1.136548822547 -0.000000000000 -1.000000000000 -1.638036840407 1.136548822547 -0.000000000000 diff --git a/Project#05/input/h2o/STO-3G/input.dat b/Project#05/input/h2o/STO-3G/input.dat deleted file mode 100644 index f8c5067..0000000 --- a/Project#05/input/h2o/STO-3G/input.dat +++ /dev/null @@ -1,12 +0,0 @@ -psi: ( - label = "H2O SCF Test Case" - memory = (10.0 MB) - wfn = scf - jobtype = oeprop - delete_tei = false - delete_oei = false - reference = rhf - basis = "STO-3G" - subgroup = c1 - zmat = ((o) (h 1 1.1) (h 1 1.1 2 104.0)) -) diff --git a/Project#05/input/h2o/STO-3G/mux.dat 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- 5 1 -0.000000000000000 - 5 2 0.000000000000000 - 5 3 0.000000000000000 - 5 4 -0.000000000000000 - 5 5 2.528731198194763 - 6 1 -0.008416383544591 - 6 2 0.070517372751001 - 6 3 0.147090913304052 - 6 4 0.114920016354202 - 6 5 -0.000000000000000 - 6 6 0.760031883566609 - 7 1 -0.008416383544591 - 7 2 0.070517372751002 - 7 3 -0.147090913304052 - 7 4 0.114920016354202 - 7 5 -0.000000000000000 - 7 6 -0.003979868621841 - 7 7 0.760031883566609 diff --git a/Project#05/input/h2o/STO-3G/v.dat b/Project#05/input/h2o/STO-3G/v.dat deleted file mode 100644 index d5b7411..0000000 --- a/Project#05/input/h2o/STO-3G/v.dat +++ /dev/null @@ -1,28 +0,0 @@ - 1 1 -61.580595358149914 - 2 1 -7.410821877330996 - 2 2 -10.009071226859687 - 3 1 0.000000000000000 - 3 2 0.000000000000000 - 3 3 -9.987550507419133 - 4 1 -0.014473835903318 - 4 2 -0.176890246723779 - 4 3 0.000000000000000 - 4 4 -9.944042952440439 - 5 1 0.000000000000000 - 5 2 0.000000000000000 - 5 3 -0.000000000000000 - 5 4 0.000000000000000 - 5 5 -9.875876065926128 - 6 1 -1.231685872788711 - 6 2 -2.977227202971528 - 6 3 -1.822241058022723 - 6 4 -1.471788274313766 - 6 5 0.000000000000000 - 6 6 -5.300202953839792 - 7 1 -1.231685872788712 - 7 2 -2.977227202971529 - 7 3 1.822241058022724 - 7 4 -1.471788274313766 - 7 5 0.000000000000001 - 7 6 -1.067166014696110 - 7 7 -5.300202953839793 diff --git a/Project#05/output/ch4/STO-3G/output.txt b/Project#05/output/ch4/STO-3G/output.txt deleted file mode 100644 index ea1c2a2..0000000 --- a/Project#05/output/ch4/STO-3G/output.txt +++ /dev/null @@ -1,37 +0,0 @@ -Escf = -39.726850324347 -Emp2 = -0.056046676165 -Etot = -39.782897000512 -iter = 1 Ecc = -0.070745263263 -iter = 2 Ecc = -0.075483796521 -iter = 3 Ecc = -0.077200328167 -iter = 4 Ecc = -0.077865987703 -iter = 5 Ecc = -0.078135369924 -iter = 6 Ecc = -0.078247914883 -iter = 7 Ecc = -0.078296205328 -iter = 8 Ecc = -0.078317411865 -iter = 9 Ecc = -0.078326913387 -iter = 10 Ecc = -0.078331243411 -iter = 11 Ecc = -0.078333244509 -iter = 12 Ecc = -0.078334179793 -iter = 13 Ecc = -0.078334620840 -iter = 14 Ecc = -0.078334830264 -iter = 15 Ecc = -0.078334930235 -iter = 16 Ecc = -0.078334978150 -iter = 17 Ecc = -0.078335001185 -iter = 18 Ecc = -0.078335012284 -iter = 19 Ecc = -0.078335017641 -iter = 20 Ecc = -0.078335020230 -iter = 21 Ecc = -0.078335021483 -iter = 22 Ecc = -0.078335022089 -iter = 23 Ecc = -0.078335022383 -iter = 24 Ecc = -0.078335022525 -iter = 25 Ecc = -0.078335022594 -iter = 26 Ecc = -0.078335022627 -iter = 27 Ecc = -0.078335022643 -iter = 28 Ecc = -0.078335022651 -iter = 29 Ecc = -0.078335022655 -iter = 30 Ecc = -0.078335022657 -iter = 31 Ecc = -0.078335022658 -CC iterations converged -Ecc = -0.078335022658 -Etot = -39.805185347005 diff --git a/Project#05/output/h2o/DZ/output.txt b/Project#05/output/h2o/DZ/output.txt deleted file mode 100644 index 3105ecd..0000000 --- a/Project#05/output/h2o/DZ/output.txt +++ /dev/null @@ -1,44 +0,0 @@ -Escf = -75.977878975377 -Emp2 = -0.152709879075 -Etot = -76.130588854452 -iter = 1 Ecc = -0.153219621639 -iter = 2 Ecc = -0.157583607713 -iter = 3 Ecc = -0.158780675351 -iter = 4 Ecc = -0.159372391348 -iter = 5 Ecc = -0.159624912154 -iter = 6 Ecc = -0.159744546198 -iter = 7 Ecc = -0.159800894442 -iter = 8 Ecc = -0.159828278264 -iter = 9 Ecc = -0.159841746027 -iter = 10 Ecc = -0.159848484750 -iter = 11 Ecc = -0.159851902014 -iter = 12 Ecc = -0.159853658806 -iter = 13 Ecc = -0.159854573327 -iter = 14 Ecc = -0.159855055123 -iter = 15 Ecc = -0.159855311795 -iter = 16 Ecc = -0.159855449966 -iter = 17 Ecc = -0.159855525065 -iter = 18 Ecc = -0.159855566244 -iter = 19 Ecc = -0.159855589005 -iter = 20 Ecc = -0.159855601678 -iter = 21 Ecc = -0.159855608780 -iter = 22 Ecc = -0.159855612784 -iter = 23 Ecc = -0.159855615052 -iter = 24 Ecc = -0.159855616344 -iter = 25 Ecc = -0.159855617082 -iter = 26 Ecc = -0.159855617505 -iter = 27 Ecc = -0.159855617749 -iter = 28 Ecc = -0.159855617890 -iter = 29 Ecc = -0.159855617971 -iter = 30 Ecc = -0.159855618018 -iter = 31 Ecc = -0.159855618046 -iter = 32 Ecc = -0.159855618062 -iter = 33 Ecc = -0.159855618071 -iter = 34 Ecc = -0.159855618077 -iter = 35 Ecc = -0.159855618080 -iter = 36 Ecc = -0.159855618082 -iter = 37 Ecc = -0.159855618083 -iter = 38 Ecc = -0.159855618083 -CC iterations converged -Ecc = -0.159855618083 -Etot = -76.137734593460 diff --git a/Project#05/output/h2o/DZP/output.txt b/Project#05/output/h2o/DZP/output.txt deleted file mode 100644 index 0eb9c42..0000000 --- a/Project#05/output/h2o/DZP/output.txt +++ /dev/null @@ -1,44 +0,0 @@ -Escf = -76.008821792901 -Emp2 = -0.222519233815 -Etot = -76.231341026716 -iter = 1 Ecc = -0.224897568695 -iter = 2 Ecc = -0.229765989813 -iter = 3 Ecc = -0.230690952187 -iter = 4 Ecc = -0.231206877752 -iter = 5 Ecc = -0.231397181303 -iter = 6 Ecc = -0.231490655906 -iter = 7 Ecc = -0.231532173950 -iter = 8 Ecc = -0.231552454278 -iter = 9 Ecc = -0.231562184987 -iter = 10 Ecc = -0.231567038587 -iter = 11 Ecc = -0.231569475351 -iter = 12 Ecc = -0.231570726044 -iter = 13 Ecc = -0.231571376449 -iter = 14 Ecc = -0.231571720404 -iter = 15 Ecc = -0.231571904849 -iter = 16 Ecc = -0.231572005163 -iter = 17 Ecc = -0.231572060412 -iter = 18 Ecc = -0.231572091200 -iter = 19 Ecc = -0.231572108536 -iter = 20 Ecc = -0.231572118390 -iter = 21 Ecc = -0.231572124037 -iter = 22 Ecc = -0.231572127296 -iter = 23 Ecc = -0.231572129188 -iter = 24 Ecc = -0.231572130292 -iter = 25 Ecc = -0.231572130940 -iter = 26 Ecc = -0.231572131321 -iter = 27 Ecc = -0.231572131546 -iter = 28 Ecc = -0.231572131679 -iter = 29 Ecc = -0.231572131758 -iter = 30 Ecc = -0.231572131805 -iter = 31 Ecc = -0.231572131833 -iter = 32 Ecc = -0.231572131849 -iter = 33 Ecc = -0.231572131859 -iter = 34 Ecc = -0.231572131865 -iter = 35 Ecc = -0.231572131869 -iter = 36 Ecc = -0.231572131871 -iter = 37 Ecc = -0.231572131872 -iter = 38 Ecc = -0.231572131873 -CC iterations converged -Ecc = -0.231572131873 -Etot = -76.240393924774 diff --git a/Project#05/output/h2o/STO-3G/output.txt b/Project#05/output/h2o/STO-3G/output.txt deleted file mode 100644 index 83bc8e4..0000000 --- a/Project#05/output/h2o/STO-3G/output.txt +++ /dev/null @@ -1,44 +0,0 @@ -Escf = -74.942079928192 -Emp2 = -0.049149636120 -Etot = -74.991229564312 -iter = 1 Ecc = -0.062758205955 -iter = 2 Ecc = -0.067396582597 -iter = 3 Ecc = -0.069224536410 -iter = 4 Ecc = -0.070007757556 -iter = 5 Ecc = -0.070360041902 -iter = 6 Ecc = -0.070523820218 -iter = 7 Ecc = -0.070602032617 -iter = 8 Ecc = -0.070640293027 -iter = 9 Ecc = -0.070659428829 -iter = 10 Ecc = -0.070669194426 -iter = 11 Ecc = -0.070674268048 -iter = 12 Ecc = -0.070676944995 -iter = 13 Ecc = -0.070678375859 -iter = 14 Ecc = -0.070679148887 -iter = 15 Ecc = -0.070679570139 -iter = 16 Ecc = -0.070679801279 -iter = 17 Ecc = -0.070679928796 -iter = 18 Ecc = -0.070679999445 -iter = 19 Ecc = -0.070680038717 -iter = 20 Ecc = -0.070680060604 -iter = 21 Ecc = -0.070680072825 -iter = 22 Ecc = -0.070680079661 -iter = 23 Ecc = -0.070680083488 -iter = 24 Ecc = -0.070680085633 -iter = 25 Ecc = -0.070680086836 -iter = 26 Ecc = -0.070680087511 -iter = 27 Ecc = -0.070680087891 -iter = 28 Ecc = -0.070680088103 -iter = 29 Ecc = -0.070680088223 -iter = 30 Ecc = -0.070680088290 -iter = 31 Ecc = -0.070680088328 -iter = 32 Ecc = -0.070680088349 -iter = 33 Ecc = -0.070680088361 -iter = 34 Ecc = -0.070680088368 -iter = 35 Ecc = -0.070680088372 -iter = 36 Ecc = -0.070680088374 -iter = 37 Ecc = -0.070680088375 -iter = 38 Ecc = -0.070680088376 -CC iterations converged -Ecc = -0.070680088376 -Etot = -75.012760016568 diff --git a/Project#06/README.md b/Project#06/README.md deleted file mode 100644 index effecf3..0000000 --- a/Project#06/README.md +++ /dev/null @@ -1,84 +0,0 @@ -# Project #6: A perturbative triples correction to CCSD: CCSD(T) - -The CCSD(T) method is often referred to as the "gold standard" of quantum chemistry for its high accuracy and reliability. The purpose of this project is to illustrate the fundamental aspects of an efficient implementation of the (T) energy correction. This project builds upon the results of -[Project #5](../Project%2305). - -The spin-orbital expression for the (T) correction, using the same notation as in -[Project #5](../Project%2305), is: - - - -where - - - -the "disconnected" triples are defined as - - - -and the "connected" triples as - - - -The three-index permutation operator is defined by its action on an algebraic function as - - - -The total energy is - - - -## Algorithm #1: Full Storage of Triples - -The most straightforward approach to evaluation of the (T) energy correction is to compute and store explicitly the connected and disconnected triples and plug them into the energy expression above. Store the triples amplitudes as six-dimensional arrays over occupied and virtual spin orbitals. - -## Algorithm #2: Avoided Storage of Triples - -Note that each T3 amplitude depends on all the T1 and T2 amplitudes, **not** on other triples. This suggests that the calculation of the T3 amplitudes appearing in the energy expression could proceed one amplitude at a time: - -``` - Loop over i - Loop over j - Loop over k - Loop over a - Loop over b - Loop over c - - Compute connected and disconnected T3 amplitudes for current i,j,k,a,b,c combination - - Calculate contribution of these T3 amplitudes to the (T) energy - - End c loop - End b loop - End a loop - End k loop - End j loop - End i loop -``` - -This algorithm reduces the storage (memory and disk) requirements of the (T) correction **considerably**. One can conceive of other approaches as well, including calculations of batches of T3 amplitudes (rather than one at a time) to improve floating-point performance. For example: - -``` - Loop over i - Loop over j - Loop over k - - Compute all T3 amplitudes (all a,b,c combinations) for current i,j,k - - Calculation contribution of these T3 amplitudes to the (T) energy - - End k loop - End j loop - End i loop -``` - -This approach requires more storage [O(v3)] than the one-at-a-time approach, but can be considerably faster for modern high-performance computers. A good discussion of the most efficient algorithm can be found in A. P. Rendell, T. J. Lee, A. Komornicki, //Chem. Phys. Lett.// **178**, 462-470 (1991). - -## Test Cases -The input structures, integrals, etc. for these examples may be found in the [input](./input) -directory, the CCSD Energies can be found in [Project #5](../Project%2305). - -* STO-3G Water | [Output](./output/h2o/STO-3G/output.txt) -* DZ Water | [Output](./output/h2o/DZ/output.txt) -* DZP Water | [Output](./output/h2o/DZP/output.txt) -* STO-3G Methane | [Output](./output/ch4/STO-3G/output.txt) diff --git a/Project#06/figures/D.png b/Project#06/figures/D.png deleted file mode 100644 index b2dd66421141d2f3b03830a991ab57936be8ec85..0000000000000000000000000000000000000000 GIT binary patch literal 0 HcmV?d00001 literal 7439 zcmZ9RcU%+8`u|Z;P((d?j`Su+&;y!;B#bbA_{`2pr{d*CW3%SR}oQq`61`t`@Q$Kf9%dYJM(^KcAuHgYo9$zz@zn77_ZRM z($dFxdlI#@7K`S~0NrKtXL`WcwfT!S8-YV;X%!~vO;eZ7*DdMZM4XnE+D1!jU!0cK zDD9rViTY($gR#;kE zx=0u-XQC(SU)|?xt{cK-GLbU?5E&V{H4?m4C}9IYa5x+QbO1OwY?*JdMXD0WsLCw@ 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iterations to converge the RMS density difference to a relatively loose threshold of 10-8. -One of the most effective methods for speeding up such iterative sequences is the -"Direct Inversion in the Iterative Subspace (DIIS)" approach, which was -[presented by Pulay](http://sirius.chem.vt.edu/wiki/lib/exe/fetch.php?media=crawdad:programming:sdoc8328.pdf) -in the 1980's. The essential idea of the DIIS approach is as follows: -if the current guess at the wave function/density matrix/Fock matrix is sufficiently close to the final (converged) result, -a new guess may be constructed as a simple linear combination of the previous few iterates, -where the coefficients of such an extrapolation are determined from Lagrangian minimization procedure. - -The purpose of this programming project is to implement the Pulay DIIS procedure within the SCF algorithm from -[Project #3](../Project%2303). - -## Working Equations - -Given a series of Fock matrices, Fi (expressed in the AO basis set), a new approximation to the converged solution may be written as - - - -by requiring that the corresponding extrapolated "error" matrix - - - -is approximately the zero matrix in a least-squares sense. The error matrix for each iteration is given by - - - -where Di is the AO-basis density matrix used to construct -Fi, and S is the AO-basis overlap matrix. Minimization of e' under the constraint that - - - -leads to the following system of linear equations for the ci: - - - -where lambda is a Lagrangian multiplier and the elements Bij are computed as dot products of error matrices: - - - -## Step #1: Compute the Error Matrix in Each Iteration - -Compute the error matrix for the current iteration using the matrix equation for ei given above. -Note that the density matrix you use must be the same one used to construct the corresponding Fock matrix. -If you print the error matrix in each iteration, you should be able to note that it gradually falls to zero as the SCF procedure converges. - -## Step #2: Build the B Matrix and Solve the Linear Equations - -After you have computed at least two error matrices, it is possible to begin the DIIS extrapolation procedure. -Compute the B matrix above for all of the current error matrices. -(Note that the matrix is symmetric, so one need only compute the lower triangle to get the entire matrix). - -Next, use a standard linear-equation solver (such as the DGESV function in the LAPACK library, -to which PSI4 has an interface named C_DGESV) to compute the ci coefficients. -(NB: If you use the LAPACK solver, or any LAPACK or BLAS function for that matter, you must use matrices allocated as contiguous memory, -as discussed in [Project #7](../Project%2307)). - -## Step #3: Compute the New Fock Matrix - -Build a new Fock matrix using the equation for F' above and continue with the SCF procedure as usual. -This implies that one must store all of the Fock matrices corresponding to each of the error matrices used in constructing the B matrix above. -Note: - - * Do **not** use the extrapolated Fock matrix to compute error matrices for subsequent DIIS steps. - * Keep only a relatively small number of error matrices; six to eight are reasonable for closed-shell SCF calculations. When the chosen number of error - matrices is exceeded delete the oldest error matrix. - -Once the procedure is complete and working correctly, you should notice a considerable reduction in the number of SCF cycles required to achieve convergence. -For example, for the STO-3G/H2O test case from [Project #3](../Project%2303), -the simple SCF algorithm converges to 10-12 in the density in 39 iterations: -``` - Iter E(elec) E(tot) Delta(E) RMS(D) - 00 -125.842077437699 -117.839710375888 - 01 -78.286583284740 -70.284216222929 47.555494152959 7.026491112304 - 02 -84.048316253435 -76.045949191625 -5.761732968695 1.586429080972 - 03 -82.716965960855 -74.714598899044 1.331350292581 0.329292871345 - 04 -82.987140757002 -74.984773695191 -0.270174796147 0.120465253222 - 05 -82.938133187513 -74.935766125703 0.049007569488 0.043060496803 - 06 -82.946271078699 -74.943904016889 -0.008137891186 0.020309423061 - 07 -82.944486784914 -74.942119723104 0.001784293785 0.009137578496 - 08 -82.944617252243 -74.942250190433 -0.000130467329 0.004460301971 - 09 -82.944503500703 -74.942136438892 0.000113751541 0.002127028935 - 10 -82.944478930626 -74.942111868815 0.000024570077 0.001026790950 - 11 -82.944461627685 -74.942094565874 0.000017302941 0.000494443064 - 12 -82.944454198375 -74.942087136565 0.000007429310 0.000238548591 - 13 -82.944450445051 -74.942083383241 0.000003753324 0.000115056300 - 14 -82.944448661686 -74.942081599876 0.000001783365 0.000055511004 - 15 -82.944447795931 -74.942080734120 0.000000865755 0.000026782106 - 16 -82.944447379017 -74.942080317206 0.000000416914 0.000012922161 - 17 -82.944447177685 -74.942080115875 0.000000201331 0.000006234890 - 18 -82.944447080565 -74.942080018755 0.000000097120 0.000003008344 - 19 -82.944447033699 -74.942079971889 0.000000046867 0.000001451536 - 20 -82.944447011086 -74.942079949276 0.000000022613 0.000000700372 - 21 -82.944447000175 -74.942079938365 0.000000010911 0.000000337933 - 22 -82.944446994911 -74.942079933100 0.000000005265 0.000000163055 - 23 -82.944446992371 -74.942079930560 0.000000002540 0.000000078675 - 24 -82.944446991145 -74.942079929335 0.000000001226 0.000000037961 - 25 -82.944446990554 -74.942079928743 0.000000000591 0.000000018316 - 26 -82.944446990268 -74.942079928458 0.000000000285 0.000000008838 - 27 -82.944446990131 -74.942079928320 0.000000000138 0.000000004264 - 28 -82.944446990064 -74.942079928254 0.000000000066 0.000000002058 - 29 -82.944446990032 -74.942079928222 0.000000000032 0.000000000993 - 30 -82.944446990017 -74.942079928206 0.000000000016 0.000000000479 - 31 -82.944446990009 -74.942079928199 0.000000000007 0.000000000231 - 32 -82.944446990005 -74.942079928195 0.000000000004 0.000000000112 - 33 -82.944446990004 -74.942079928193 0.000000000002 0.000000000054 - 34 -82.944446990003 -74.942079928193 0.000000000001 0.000000000026 - 35 -82.944446990002 -74.942079928192 0.000000000000 0.000000000013 - 36 -82.944446990002 -74.942079928192 0.000000000000 0.000000000006 - 37 -82.944446990002 -74.942079928192 0.000000000000 0.000000000003 - 38 -82.944446990002 -74.942079928192 0.000000000000 0.000000000001 - 39 -82.944446990002 -74.942079928192 0.000000000000 0.000000000001 -``` - -With DIIS extrapolation using six error matrices, this is reduced to only ten iterations: - -``` - Iter E(elec) E(tot) Delta(E) RMS(D) - 00 -125.842077437699 -117.839710375888 - 01 -78.286583284740 -70.284216222929 47.555494152959 7.026491112304 - 02 -82.579039780737 -74.576672718926 -4.292456495997 1.366619501600 - 03 -83.108076865885 -75.105709804074 -0.529037085148 0.349635242477 - 04 -82.957022995474 -74.954655933663 0.151053870411 0.082112373912 - 05 -82.941311458592 -74.938944396782 0.015711536881 0.045048744784 - 06 -82.944472996531 -74.942105934721 -0.003161537939 0.001798803069 - 07 -82.944447027029 -74.942079965219 0.000025969502 0.000003764196 - 08 -82.944446990675 -74.942079928865 0.000000036354 0.000000202704 - 09 -82.944446990002 -74.942079928192 0.000000000673 0.000000001127 - 10 -82.944446990002 -74.942079928192 0.000000000000 0.000000000000 -``` - -## References - - * P. Pulay, "Convergence Acceleration of Iterative Sequences. The Case of the SCF Iteration", *Chem. Phys. Lett.* **73**, 393-398 (1980). - * P. Pulay, "Improved SCF Convergence Acceleration", *J. Comp. Chem.* **3**, 556-560 (1982). - * T. P. Hamilton and P. Pulay, "Direct Inversion in the Iterative Subspace (DIIS) Optimization of Open-Shell, Excited-State, - and Small Multiconfiguration SCF Wave functions", *J. Chem. 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z2Bh<_wSY0Ss6-5eGSr6*B5T+~r5Y${6XyU`e~-Bn_yHYp)Du~x_~>rD{F0{0?z@hL zuMu=ZatF`a=lC&S%5nF)q_EB_7~f@9f55>zEY}FmtB;PVb)=*NS2)`MfUB7%zUgWk*+UJ$bg}R0hNYs-r3)q-g-ud*J^6f4 zTaSV;=-eFhCVgg*lHLboYo(Ro_Y68jo>Ts$b?rn*!RcL5j(C%@M2XtUFP1v(=2=e2lnMLRXh`og3`p0f$l(NZ>l+NbwTW7T07RLO@%`H$fSO=j! z|nU($nekFY17H$q#Gp3AMDXW`2a za@9=9h>pRk)BwJ4J$G!=Z_Q9WFumw3)3WMH`0XUdqZgl3x)L)+4zhz_L=CfRe}Sr_ zCO5opRG(6_;`v!r0M!k1X%{JS{Bt@LILJ$sFqG02kNh{khiW)UfmVl3YyI)PskTE+ zWCd{62sQSy;=CE1lahIHZ8fawQ8-OF#zuk-QynR$zQh5^wa|f?u7|8<uL4A=0y- znj0y>TFBUMBKy8bI&;2Av#uV4A6;@%JVi#tkfI>=+pOckZHEY;QjH%ONUCA|)-1L0 z!XEARR;ZayBc?rNEFMX|w!z*wLv&MiLQ{gKqqEiDn*#&{#QhJ?i!u@lXPwzH~$E@{yPMcGwMo;(;#(v zZHXxg<)$Ot4#f5O^nOP%cTRF7K7@3tk8yO>5klFzjZ=Sg#Rt~v8B^DDHm{A;dkOH) g-f((dtjWElN6AKSii2h and its subgroups -- which means that higher symmetry structures can yield up to a factor of 64 reduction in the computational costs. - -The purpose of this project is to take advantage of basic point-group symmetry in an SCF calculation. -While the most efficient programs will store only the symmetry-allowed sets of two-electron integrals, -for the purposes of this project we'll deal only with the one-electron (two-index) components. - -## Background - -The vanishing integral rule of point-group theory may be stated as follows for Abelian groups: - - - -where ΓX denotes the irreducible representation (irrep) of entity X. -That is, unless the direct product of the irreps of the functions or operators in the integrand contains the totally symmetric irrep, the integral must be zero. - -The vanishing integral rule of group theory may be readily applied to the various integrals and wave-function parameters in the SCF procedure -if the AO-basis functions over which the they are evaluated have been properly symmetrized -[i.e. used to form symmetry-adapted linear combinations, normally referred to as symmetry orbitals (SOs)]. - -For example, consider the H2O test case with the STO-3G basis set as given in [Project #3](../Project%2303). The AO -([contracted Gaussian](http://sirius.chem.vt.edu/wiki/lib/exe/fetch.php?media=basis_sets.pdf)) basis functions -on the oxygen atom consist of 1s, 2s, 2px, 2py, and 2pz orbitals, -which those for each hydrogen atom consist of only the 1s, giving a total of seven AOs. -If we take oxygen to be the first atom and ignore the C2v point group symmetry of the molecule, -the resulting overlap integral matrix looks like: - -``` - 1 2 3 4 5 6 7 - - 1 1.0000000 0.2367039 -0.0000000 -0.0000000 -0.0000000 0.0384056 0.0384056 - 2 0.2367039 1.0000000 0.0000000 -0.0000000 0.0000000 0.3861388 0.3861388 - 3 -0.0000000 0.0000000 1.0000000 -0.0000000 0.0000000 0.2684382 -0.2684382 - 4 -0.0000000 -0.0000000 -0.0000000 1.0000000 -0.0000000 0.2097269 0.2097269 - 5 -0.0000000 0.0000000 0.0000000 -0.0000000 1.0000000 -0.0000000 -0.0000000 - 6 0.0384056 0.3861388 0.2684382 0.2097269 -0.0000000 1.0000000 0.1817599 - 7 0.0384056 0.3861388 -0.2684382 0.2097269 -0.0000000 0.1817599 1.0000000 -``` -The first five row/column indices correspond to the basis functions on the oxygen (in the order listed above), -while rows/columns six and seven correspond to the basis functions on each hydrogen. -Thus, the 1-2 element is the overlap integral between the 1s and 2s orbitals on the oxygen, -while element 3-7 is the overlap integral between the oxygen 2px orbital and the second hydrogen 1s orbital. - -Points to note about this matrix: - - The 1s and 2s orbitals on oxygen are not orthogonal to one another, but both are orthogonal to all three p-type orbitals. - This occurs because, in Cartesian Gaussian basis sets, - orthogonality is generally obtained only between functions of different angular momenta on the same atomic center. - - The 1s orbitals on the hydrogens have the same overlap integral (to within a sign) - with all the orbitals on the oxygen because they are symmetry equivalent. - However, the 1s orbitals alone do not transform as irreps of the C2v point group. - - The hydrogen 1s orbitals are orthogonal to the 2pz orbital on the oxygen (cf. elements 5-6 and 5-7). - This is because the water molecule was arbitrarily oriented in the xy-plane to compute the above integrals; - thus the 2pz orbital is perpendicular to the molecular plane containing the hydrogen 1s orbitals. - -What happens if we turn on symmetry, i.e. take linear combinations of the AO to obtain SOs? -If we orient the molecule oriented in the yz-plane, so that the z-axis corresponds to the C2 rotation axis, -we find that the AOs transform as the following irreps: - -| SO | Irrep | -|------|--------| -| O 1s | A1 | -| O 2s | A1 | -| O 2px | B1 | -| O 2py | B2 | -| O 2pz | A1 | -| H1 1s + H2 1s | A1 | -| H1 1s - H2 1s | B2 | - -Thus, after symmetrization, there are four A1 SOs, one B1 SO, and two B2 SOs. -(The STO-3G basis set contains no A2 orbitals. One must include at least d-type functions on the oxygen and/or -p-type functions on the hydrogens to obtain A2 orbitals.) Note that a normalization factor of 1/sqrt(2) should be included for the H 1s SOs above. - -In the SO basis, the overlap integral matrix becomes: -``` - 1 2 3 4 5 6 7 - - 1 1.0000000 0.2367039 -0.0000000 0.0543137 0.0000000 0.0000000 0.0000000 - 2 0.2367039 1.0000000 -0.0000000 0.5460828 0.0000000 0.0000000 0.0000000 - 3 -0.0000000 -0.0000000 1.0000000 0.2965987 0.0000000 0.0000000 0.0000000 - 4 0.0543137 0.5460828 0.2965987 1.1817599 0.0000000 0.0000000 0.0000000 - 5 0.0000000 0.0000000 0.0000000 0.0000000 1.0000000 0.0000000 0.0000000 - 6 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 1.0000000 0.3796290 - 7 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.3796290 0.8182401 -``` - -Points to note about this matrix: - - The matrix now has a block-diagonal structure, with 4x4, 1x1, and 2x2 sub-matrices, corresponding to the A1, B1, and B2 irreps, - respectively. All off-diagonal blocks correspond to overlaps between SOs of different irreps, which must be zero according to the vanishing integral rule. - - There is only one B1 SO (the O 2px orbital), and it is normalized. - - The oxygen 1s and 2s orbitals are still orthogonal to the oxygen 2pz because they are functions of different angular momentum on the same atomic center. - - The same block-diagonal structure will appear for the kinetic-energy (T), one-electron potential-energy (V), and core Hamiltonian (H) integrals. - -## Obtaining Symmetry Information from PSI - -The PSI checkpoint file contains a great deal of useful symmetry information. To convert your SCF program to make use of symmetry, two key pieces of information are: - * The number of irreps in the molecular point group. Use the `chkpt_rd_nirreps()` function to retrieve this integer. - * The number of SOs per irrep, available as an integer array from the `chkpt_rd_sopi()` function. - -## Storing One-Electron Integrals with Symmetry - -The block-diagonal structure above implies that one need only store and use the sub-matrices of the integrals rather than the full matrix. -One way of doing this is to store the one-electron integrals as an array of smaller matrices, -the size of which is dictated by the number of SOs per irrep. For example, here's a code snippet that will extract the one-electron integrals -from the appropriate file (as was done in [Project #7](../Project%2307) ), -but stores them in an array of matrices: - -```c++ - int ntri, nirreps; - double *scratch; - double ***S; - ... - ntri = nso*(nso+1)/2; - scratch = init_array(ntri); - ... - symm_offset = init_int_array(nirreps); - for(h=1; h < nirreps; h++) symm_offset[h] = symm_offset[h-1] + sopi[h-1]; - ... - /* overlap integrals */ - S = (double ***) malloc(nirreps*sizeof(double **)); - stat = iwl_rdone(PSIF_OEI, PSIF_SO_S, scratch, ntri, 0, 0, outfile); - for(h=0; h < nirreps; h++) { - S[h] = block_matrix(sopi[h], sopi[h]); - for(i=0; i < sopi[h]; i++) - for(j=0; j <= i; j++) { - ij = INDEX(i+symm_offset[h],j+symm_offset[h]); - S[h][i][j] = S[h][j][i] = scratch[ij]; - } - } -``` - -Notice how S is now a `double ***` -- i.e. an array of matrices. This code uses the same `INDEX()` function found in -[Project #3](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2303), -and the sopi array is the integer array of SOs per irrep obtained using the `chkpt_rd_sopi()` function. -The `symm_offset` array is useful for converting between relative orbital indices and absolute orbital indices. -(For example, orbital 0 in the B2 irrep block corresponds to orbital 5 -in the full list of orbitals; the first number is the relative index, the second is the absolute index.) - -## Multiplication of Matrices with Symmetry - -If we store the integral, MO coefficient, density, and Fock matrices in the block-diagonal structure described above, -we may compute matrix products of these quantities separately for each diagonal block. For example, the matrix product may be written as: - - - -where *h* denotes a particular irrep of the point group and Ch denotes the *h*-th irrep subblock of the full matrix C. -(The notation of the large plus with a circle around it indicates a direct sum.) - -## Occupied Orbitals and the Density Matrix - -The calculation of the density matrix requires information about the number of occupied orbitals: - - - -In a calculation without symmetry, one need only know the number of electrons (equivalently, the atomic numbers of the atoms and the overall molecular charge) -to evaluate this expression. However, if the density and MO coefficient matrices are stored in symmetry-blocked form, -as above, one needs to know the number of occupied MOs in each irrep. - -For the case of the C2v water molecule, which has two σ O-H bonds, two oxygen lone pairs, -and one oxygen core orbital, the orbital occupations are not difficult to determine, given the above information about the number of SOs in each irrep. -Since the MOs are constructed as linear combinations of the SOs, and only SOs of the same irrep can combine, we may rationalize the occupied orbitals of -H2O as follows: - -| Occupied MO | Irrep | Description | -|---------------|----------|-------------| -| O 1s | A1 | Oxygen Core | -| O 2s + (H1 1s + H2 1s) | A1 | Symmetric Combination of O-H σ Bonds | -| O 2pz | A1 | In-Plane Oxygen Lone Pair | -| O 2px | B1 | Out-of-Plane Oxygen Lone Pair | -| O 2py + (H1 1s - H2 1s) | B2 | Antisymmetric Combination of O-H σ Bonds | - -Thus, for the water molecule, there are 3 A1, 1 B1, and 1 B2 occupied orbitals. - -Determining the occupations automatically is sometimes a difficult task, especially for molecules with unusual bonding patterns. -Many SCF programs will simply take the core Hamiltonian matrix (often used as the initial guess for the Fock matrix), -diagonalize it (in the othogonal AO basis) in each irrep block, and identify the lowest eigenvalues in each irrep as occupied. -However, this approach often fails for many molecules (especially those with open shells) because of near-degeneracies -that may not be adequately described by the simple core Hamiltonian. Thus, some programs will make use of more -sophisticated guesses at the Fock matrix, e.g. Hueckel orbitals or other (semi)empirical forms. - -## Building the Fock Matrix - -The only portion of the SCF procedure involving two-electron integrals is the Fock-matrix build: - - - -where the notation used in [Project #3](../Project%2303) is retained above. -If the Fock matrix and density matrix are stored in a symmetry-blocked manner similar to the overlap matrix above, -then one may limit the corresponding loops only to the symmetry-allowed combinations, e.g. the irreps of μ and -ν must match for Fμν to be non-zero and the irreps of λ -and σ must match for Dλσ to be non-zero. -Note, however, that, because of the symmetries in the two-electron integrals, -the irrep of λ and σ do not necessarily have to match that of μ and ν. - - * [Hint](./hints/hint1.md): Fock-Build Code diff --git a/Project#09/figures/density-matrix.png b/Project#09/figures/density-matrix.png deleted file mode 100644 index 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zwMQvy=H7=c!miIG=ckr8Z)sMTUpAQUql56{OYWWTu+cGzTd-{LDr|Jz*{w|VMb~NF z*vX~^@$P%tJJQqAEc9E>N~v?gW@a*Aa`Z&5?s%@%&4gt}^GWW(SC>Fdb1MdGXuB@G zmE`l1_f)?NLASxVwELCiI{yl%Ab|A@8suUO_~){R$2Iya<_YQZDUL{_|fGr%HDH;oKk zPd&!K=6z8IUE8u^?_8LO&kG+_sbY20h7yy^wXJ4mJnE}fR;Xgl(0lh8jkltwFz`81 zcZa@qv1DEQ8&>S#5dCks{{*MAJJsB@;bPIes?BCC>BBa&`ZWOHi6vtS(ZNao1NA%w AxBvhE diff --git a/Project#09/hints/hint1.md b/Project#09/hints/hint1.md deleted file mode 100644 index 670bf7d..0000000 --- a/Project#09/hints/hint1.md +++ /dev/null @@ -1,28 +0,0 @@ -```c++ - for(h=0; h < nirreps; h++) { - for(i=0; i < sopi[h]; i++) { - I = symm_offset[h] + i; - for(j=0; j < sopi[h]; j++) { - J = symm_offset[h] + j; - F[h][i][j] = H[h][i][j]; - - for(g=0; g < nirreps; g++) { - for(k=0; k < sopi[g]; k++) { - K = symm_offset[g] + k; - for(l=0; l < sopi[g]; l++) { - L = symm_offset[g] + l; - - ij = INDEX(I,J); kl = INDEX(K,L); - ijkl = INDEX(ij,kl); - ik = INDEX(I,K); jl = INDEX(J,L); - ikjl = INDEX(ik,jl); - - F[h][i][j] += D[g][k][l] * (2.0 * TEI[ijkl] - TEI[ikjl]); - } - } - - } - } - } - } -``` diff --git a/Project#10/README.md b/Project#10/README.md deleted file mode 100644 index 48e85fe..0000000 --- a/Project#10/README.md +++ /dev/null @@ -1,119 +0,0 @@ -# Project #10: DIIS extrapolation for solving the CC amplitude equations -In an earlier project, we examined how DIIS ("direct inversion in the iterative -subspace") can reduce substantially the number of iterations required to converge the -self-consistent field. In this project, we examine how DIIS can similarly speed -convergence in the CC amplitude equations. This approach was first used by Scuseria, -Lee, and Schaefer in 1986 ["Accelerating the conference of the coupled-cluster -approach. The use of the DIIS method", *Chem. Phys. Lett.* **130**, 236 (1986)]. - -## Error Vectors -The DIIS approach requires a well-defined "error vector", a quantity that approaches -zero as the equations converge. In the SCF procedure, we use the atomic-orbital -representation of the occupied-virtual block of the Fock matrix. In the CC method, we -could choose the difference between successive sets of cluster amplitudes: - - - -where Ti represents a vector containing all the cluster amplitudes for the *i*-th iteration. - -There are three important points to note about this choice of error vector: - * Defining the error vectors as differences between successive sets of amplitudes - implies that one cannot begin the DIIS extrapolation until at least three - iterations are complete. - * Just as in the SCF DIIS procedure, error vectors should only be computed using - non-extrapolated sets of cluster amplitudes. - * The set of cluster amplitudes can require substantial memory for larger - molecules; hence, the choice of the number of error vectors used in the CC DIIS - procedure is potentially dependent on the available storage (disk and memory). - -## Extrapolation -Given the above definition of the error vectors, the set of linear equations to be solved is the same as that for the SCF DIIS procedure: - - - -where λ is a Lagrangian multiplier and the elements Bij are computed as dot products of error matrices: - - - -A new set of cluster amplitudes is then obtained as a linear combinations of older amplitudes using the coefficients from the linear equations above: - - - -Again: The extrapolated cluster amplitudes should be used only in the CC amplitude equations, not to compute subsequent error vectors. - -## Results -Once the procedure is working, you should observe a considerable reduction in the -number of iterations required to converge the CC amplitude equations to a given -tolerance. For example, without DIIS extrapolation, the STO-3G H2O test -case from [Project #5](../Project%2305) converges in 38 iterations to a -precision of 10-12: - -``` -iter = 1 Ecc = -0.062758205955 -iter = 2 Ecc = -0.067396582597 -iter = 3 Ecc = -0.069224536410 -iter = 4 Ecc = -0.070007757556 -iter = 5 Ecc = -0.070360041902 -iter = 6 Ecc = -0.070523820218 -iter = 7 Ecc = -0.070602032617 -iter = 8 Ecc = -0.070640293027 -iter = 9 Ecc = -0.070659428829 -iter = 10 Ecc = -0.070669194426 -iter = 11 Ecc = -0.070674268048 -iter = 12 Ecc = -0.070676944995 -iter = 13 Ecc = -0.070678375859 -iter = 14 Ecc = -0.070679148887 -iter = 15 Ecc = -0.070679570139 -iter = 16 Ecc = -0.070679801279 -iter = 17 Ecc = -0.070679928796 -iter = 18 Ecc = -0.070679999445 -iter = 19 Ecc = -0.070680038717 -iter = 20 Ecc = -0.070680060604 -iter = 21 Ecc = -0.070680072825 -iter = 22 Ecc = -0.070680079661 -iter = 23 Ecc = -0.070680083488 -iter = 24 Ecc = -0.070680085633 -iter = 25 Ecc = -0.070680086836 -iter = 26 Ecc = -0.070680087511 -iter = 27 Ecc = -0.070680087891 -iter = 28 Ecc = -0.070680088103 -iter = 29 Ecc = -0.070680088223 -iter = 30 Ecc = -0.070680088290 -iter = 31 Ecc = -0.070680088328 -iter = 32 Ecc = -0.070680088349 -iter = 33 Ecc = -0.070680088361 -iter = 34 Ecc = -0.070680088368 -iter = 35 Ecc = -0.070680088372 -iter = 36 Ecc = -0.070680088374 -iter = 37 Ecc = -0.070680088375 -iter = 38 Ecc = -0.070680088376 -``` - -The DIIS extrapolation with eight error vectors reduces the number of iterations to just 16: - -``` -iter = 1 Ecc = -0.062758205955 -iter = 2 Ecc = -0.067396582597 -iter = 3 Ecc = -0.070325967097 -iter = 4 Ecc = -0.070642541851 -iter = 5 Ecc = -0.070681441999 -iter = 6 Ecc = -0.070679216733 -iter = 7 Ecc = -0.070680252965 -iter = 8 Ecc = -0.070680084062 -iter = 9 Ecc = -0.070680084577 -iter = 10 Ecc = -0.070680089084 -iter = 11 Ecc = -0.070680088015 -iter = 12 Ecc = -0.070680088239 -iter = 13 Ecc = -0.070680088359 -iter = 14 Ecc = -0.070680088381 -iter = 15 Ecc = -0.070680088377 -iter = 16 Ecc = -0.070680088376 -``` - - -## Additional Reading - * G.E. Scuseria, T.J. Lee, and H.F. Schaefer, "Accelerating the conference of the - coupled-cluster approach. The use of the DIIS method", *Chem. Phys. Lett.* - **130**, 236 (1986). - * G.D. Purvis and R.J. Bartlett, "The reduced linear equation method in coupled - cluster theory", *J. Chem. 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As described -in [Project #3](../Project%2303), a simple algorithm for evaluating this matrix is: - -```cpp -for(i=0; i < nao; i++) - for(j=0; j < nao; j++) { - F[i][j] = H[i][j]; - for(k=0; k < nao; k++) - for(l=0; l < nao; l++) { - ij = INDEX(i,j); - kl = INDEX(k,l); - ijkl = INDEX(ij,kl); - ik = INDEX(i,k); - jl = INDEX(j,l); - ikjl = INDEX(ik,jl); - - F[i][j] += D[k][l] * (2.0 * TEI[ijkl] - TEI[ikjl]); - } - } -``` - -This algorithm hinges on the fact that all the two-electron integrals are -immediately available in the TEI array (which takes advantage of permutational -symmetry). In [Project #7](../Project%2307) you made use of the following code, -which reads the integrals into the TEI array in batches (sometimes referred to -in PSI as "buffers"): - -```cpp - iwl_buf_init(&InBuf, PSIF_SO_TEI, 1e-14, 1, 0); - do { - iwl_buf_fetch(&InBuf); - lblptr = InBuf.labels; - valptr = InBuf.values; - lastbuf = InBuf.lastbuf; - for(idx=4*InBuf.idx; InBuf.idx < InBuf.inbuf; InBuf.idx++) { - i = abs((int) lblptr[idx++]); - j = (int) lblptr[idx++]; - k = (int) lblptr[idx++]; - l = (int) lblptr[idx++]; - ij = INDEX(i,j); - kl = INDEX(k,l); - ijkl = INDEX(ij,kl); - TEI[ijkl] = (double) valptr[InBuf.idx]; - } - } while (!lastbuf); - iwl_buf_close(&InBuf, 1); -``` - -The basic idea behind an out-of-core Fock-build code is to read the -two-electron integrals in batches and make use of each batch immediately before -moving to the next batch. Thus, the above code would be moved into the SCF -iterative procedure and modified appropriately to compute the contribution of -each individual integral to the Fock matrix: - -```cpp - iwl_buf_init(&InBuf, PSIF_SO_TEI, 1e-14, 1, 0); - do { - iwl_buf_fetch(&InBuf); - lblptr = InBuf.labels; - valptr = InBuf.values; - lastbuf = InBuf.lastbuf; - for(idx=4*InBuf.idx; InBuf.idx < InBuf.inbuf; InBuf.idx++) { - i = abs((int) lblptr[idx++]); - j = (int) lblptr[idx++]; - k = (int) lblptr[idx++]; - l = (int) lblptr[idx++]; - - integral = (double) valptr[InBuf.idx]; - - /* Compute the contribution of this integral to the Fock matrix */ - - } - } while (!lastbuf); - iwl_buf_close(&InBuf, 1); -``` - -Thus a given integral, (ij|kl), would contribute to at least two Fock matrix elements as: - - - -and - - - -## Handling Permutational Symmetry - -The most difficult aspect of the out-of-core algorithm is the fact that file contains only the permutationally unique integrals, -*(ij|kl)*, such that: - - - -where - - - -Thus, when determining the contribution of a given integral to various elements -of the Fock matrix, one must consider all possible unique permutations of the -indices, *i*, *j*, *k*, and *l*. Note, however, that coincidences among the -indices can limit the number of possibilities. For example, if one encountered -the integral *(22|11)*, it would contribute to a total of four Fock -matrix elements, viz. - - - -All such cases must be included in the algorithm to obtain a correct Fock matrix. - -## Additional Reading - * J. Almlof, K. Faegri, and K. Korsell, "Principles for a Direct SCF Approach to LCAO-MO *Ab Initio* Calculations," *J. Comp. 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zUnF|EurRs9yp;Novu3iB%Ga&3Z1SlGGT(DEGAc^M{Nh+oXLu(jtb>wq1t<8_nDOZ2 z!ewdinifBG{c?q+$ec-kzBY06ew=GY?nqJ1vKvjx!wWRdPM_UQc!v|uUWEAsdM9mt zF3UU7_GskKqns!U`UXPR<2ePTz}FXEsPDeJ9~b>w^x+??PJd4x6s%lw^x*1s9!{!1 zvu97&?yM!&#Gm?{MqM*}ps(ugk+ijplZN9CbyUHv^6zf9k-jc^KeWoY%34=U^dd*0Kf6C|RG0E11 zQJVW0ajU~Gqq@~)Q}Nj>{e?v?+ZWS=t=k9Y(nxNDzs&hIWd}a|+gX - -where *m* identifies the various excited states, and we will use *i* and *j* -(*a* and *b*) to denote occupied (unoccupied) spin-orbitals. Inserting this -into the Schrödinger equation and left-projecting onto a -particular singly excited determinant gives - - - -If we recognize that we have one of these equations for every combination of -*i* and *a* spin-orbitals, then this equation may be viewed as a matrix -eigenvalue problem: - - - -To solve this equation, we need an expression for the matrix elements in terms -of things we already know, i.e. Fock matrix elements and two-electron -integrals. This can be done using either algebraic or diagrammatic techniques -to obtain (in the spin-orbital notation of previous projects): - - - -Our task is then relatively simple: Build the Hamiltonian matrix (expressed in -the basis of all singly excited determinants) using the above expression and -diagonalize it. Note that the CIS Hamiltonian matrix is symmetric (check for -yourself by swapping *i/a* and *j/b*), with dimensions of the number of -occupied orbitals times the number of unoccupied orbitals. For our -STO-3G/H2O test case, with its ten occupied and four unoccupied -spin-orbitals, the matrix will be 40 x 40. - - * [Hint](./hints/hint1.md): CIS Hamiltonian for STO-3G H2O - -Make sure you can compute the correct CIS excitation energies for each of the -four test cases provided at the end of the page. Before you move on to the -next section, can you explain the degeneracies appearing in the -excitation-energy list? - -## Spin Adaptation of CIS - -If you carefully examine the list of eigenvalues you computed above, you will -notice a pattern: some of the eigenvalues are unique (i.e., they occur only -once), while others appear in groups of three. The former correspond to -spin-singlet excited states and the latter to spin-triplets, and all are -eigenfunctions of the S2 and Sz operators by virtue of -the fact that the spin-restricted Hartree-Fock reference wave function is such -an eigenfunction (by design, of course) and that the single-excitation -operators must yield identical amplitudes (to within a sign) for both -α- and β-spin excitations. - -Consider the structure of the singlet and triplet determinantal wave functions -from a simple two-electron/two-orbital example (such as the *1s 2s* excited -state configuration of the He atom). One can easily show that the four -possible determinants arising from this configuration, - - - -are components of one singlet and one triplet in the following combinations: - - - - - -where the superscript is the spin multiplicity (*2S+1*) and the subscript is -the *MS* value of the wave function. So, if we wanted to compute -only the eigenvalues and eigenfunctions corresponding spin singlets in our CIS -calculation, we could introduce the restriction on our CIS coefficients that α -and β excitations involving the same spatial orbitals -must be identical (including the sign). Similarly, if we wanted only triplets, -we could require that the α and β excitations -have the same magnitude but opposite signs. - -Let's begin with the singlets. Starting from the spin-orbital eigenvalue -expression and the equation for the CIS Hamiltonian matrix elements in the -previous section, we may write a spin-factored equation for the α -coefficients as - - - -Note that the mix-spin cases (where *j=*α and -*b=*β or *vice versa*) do not contribute since the Fock -matrix elements and two-electron integrals must all give zero. If we then -carry out spin integration on the integrals in the above expression and assume -that the α and β CI coefficients are -identical for the same spatial orbitals, i.e., - - - -we obtain the spatial orbital expression - - - -The part in brackets above is an expression for the spatial-orbital CIS -Hamiltonian, spin-adapted for singlet excited states, and diagonalization of -this matrix will yield only the singlet eigenvalues you obtained from your -spin-orbital matrix earlier. - - * [Hint](./hints/hint2.md): Spin-adapted CIS singlet Hamiltonian for STO-3G H2O - -How about the triplets? We use exactly the same spin-factorization, but -instead require - - - -This yields a slightly simpler Hamiltonian: - - - -which, upon diagonalization, will yield only the triplet eigenvalues (but each only occurring once) from your earlier diagonalziation. - -Why should we worry about spin adaptation? Because the dimension of the -spatial-orbital Hamiltonian matrix is **half** that of the spin-orbital -Hamiltonian, which is a factor of **four** savings in the storage of the matrix -and a factor of **eight** in the diagonalization. For large basis sets and/or -large molecules, this is a considerable computational savings and essential for -production-level codes. - -Make sure you can implement the spin-adapted CIS approach entirely in spatial -orbitals and obtain the correct excitation energies so that you can take -advantage of this greater efficiency available in this formulation. (NB: For -the CH4 test case below, you still get groups of three excitation -energies in the spin-adapted formulation. Do you understand why this -degeneracy arises?) - -## Time-Dependent Hartree Fock (TDHF)/The Random Phase Approximation (RPA) - -The TDHF/RPA approach is closely related to CIS in that only singles are -involved in the wave function expansion, except that both excitation and -"de-excitation" operators are involved. (It is probably better to view the -TDHF/RPA wave function expansion in terms of orbital rotations instead of -Slater determinants, but that's a discussion for another day.) The TDHF/RPA -eigenvalue equations take the form - - - -The definition of the ***A*** matrix is just the CIS matrix itself, *viz.* - - - -while **X** and **Y** are the parameters of single excitations and -de-excitations, respectively, and the ***B*** matrix is simply - - - -Thus, the row/column dimension of the TDHF/RPA Hamiltonian is twice that of the -CIS Hamiltonian, and the matrix is non-symmetric (so you must be careful about -the diagonalization function you choose). Do you obtain twice as many -excitation energies? - - * [Hint](./hints/hint3.md): TDHF/RPA Hamiltonian for STO-3G H2O - -## A Better Approach to Solving the TDHF/RPA Eigenvalue Equations - -Instead of solving the full-dimensional TDHF/RPA equations, which, as noted -above, is twice the size of the CIS problem (and thus four times the -Hamiltonian storage cost), one can rearrange the eigenvalue equations. First -write eigenvalue equation two separate equations, each in terms of the -submatrices **A** and **B**: - - - -and - - - -Now take +/- combinations of these equations to obtain - - - -and - - - -Solve for ***(X+Y)*** in the second equation: - - - -Insert this result into the first equation, rearrange a bit, and finally -obtain: - - - -This is an eigenvalue equation of the same dimension as the CIS eigenvalue -equation (number of occupied orbitals times number of unoccupied orbitals), -where the eigenvalue is the square of the excitation energy and the eigenvector -is ***X-Y*** . - -Make sure you can get the same set of excitation energies using the -full-dimensional TDHF/RPA approach above, as well as this reduced-dimension -approach, for all four test cases below. - -## Test Cases -The input structures, integrals, etc. for these examples may be found in the -[input directory](./input). - -| Test Case | CIS | RPA (Method 1) | RPA (Method 2) | -|-----------|-----|----------------|----------------| -| STO-3G Water | [output](./output/h2o/STO-3G/output_cis.txt) | [output](./output/h2o/STO-3G/output_rpa1.txt) | [output](./output/h2o/STO-3G/output_rpa2.txt) | -| DZ Water | [output](./output/h2o/DZ/output_cis.txt) | [output](./output/h2o/DZ/output_rpa1.txt) | [output](./output/h2o/DZ/output_rpa2.txt) | -| DZP Water | [output](./output/h2o/DZP/output_cis.txt) | [output](./output/h2o/DZP/output_rpa1.txt) | [output](./output/h2o/DZP/output_rpa2.txt) | -| STO-3G Methane | [output](./output/ch4/STO-3G/output_cis.txt) | [output](./output/ch4/STO-3G/output_rpa1.txt) | [output](./output/ch4/STO-3G/output_rpa2.txt) | - diff --git a/Project#12/figures/A-matrix.png b/Project#12/figures/A-matrix.png deleted file mode 100644 index 12867fa34fa74b7861286687691372a72566ba8f..0000000000000000000000000000000000000000 GIT binary patch literal 0 HcmV?d00001 literal 10160 zcmZ8{c_38Z`@fQSr<68JijYLaI91`;qT!%+e(3zC(SR6imiA)(4} za8kj-k^gSKUsIEGX0d200Dy;whpdN!ER{h703i?vKu#VYFE6vNA;a{fuim8?#LuCTxcv8Dn;U7xOVnbHcL%X@?RbO=lI7?M~=(?>xshrw_E!T0{(Re0F;#j z{0Do#sp`L^D#lDl28`K3v92Xq~PVCPl74ZT#Ok`N=Rp%AseN{R&ykJyExE`HqW=e!A1C-5yc!-mtG##wOCd)zC(f|hn1ORaaFty-BprR4j zOOC=(G~j6J{sV%dyVG@v@?bQAWn$t*ki)?7Y%;+fLUd9vqG>r}lqt%r{Ti7LAu~lLwi%E9*$*i#!}*d6dl-JbUaZWNOA)b zjqK#@SqvQm7G95Sjzo}MNQy2fED7bwVAHhz2`oyQg3}?=O<<;2A_?hXKzGAAYJw?f zm?_Is*VU6m)u9<7C@^`v5ki?_q$LNFV>u8!Fcdfz=n2;RC$J=4PqKm?RNlnh35anw zcOvLGDHH7xMjl>B098+iW2_JLRJJFP4X6ksCezLYKqNRCz@71W#s+XlEQIElbP5*!}oIMX8*VBYy?!dCMBcPNJ#ta%0 zY);lf$$7dsIf7uWct?*vAcj~IysnczTA#oqx$EF*6c`d~&!Q8&%v@+xmZCCHAA=?9 z8kxeKz%&ySo#-HEXG}nYc4Uev8={XT=^5*T73pNWwhqvMV2sp8qA6^Iyoa%;0>VHO3_!q4 zo%H^IXdBTfbQa2t1Xff6v4C(7h_R~)i0DeON7_?d=mZx7M=xgrQ-Q>gmi9EW_aGza z7>XAKCanZjRv>FCXuPe9OpkEcE%t@PkU*U8<>T{xoWwxT|rbDR-bII??`q* zP&r0mj6GR_#**8gQ$&EBmb)nvOfXioa|2_HSvVZw4+zuM)QF&G$7VU&0kp{S91snR zk^_TWuy{RBptGW`J&5gPXl!7HGRF|LU2$*+78LDBLI9L?pi~bS^q-i(=um_gRh!~r z=uX7iL!o+9l$nRVI}zywwR6;zSJt#sggGc{DuJ{WJfKcQ9Ve)VG?d^@GzLJCY^a;` zA4{MP(wf@Jn(iQ|GS$Py-dxj_^g6edk{adb9uFr+zQsVpK{$=S}p1!3Uw#}YS9B2HJ4>7b(zw=)FlzyKVw zi;|`^*nz2K^hZJU4{!VzL;Ra{R002@qW?op|M1=)=|1tPA5jJTheXwn+^?R5adC+^ z>A;~zoC9;o)wzx+lg89qLfyRvkyqS;4$@1nk&pgDAjyY<690A`4u+>Zbx&{J;69{( z6v?em=GKQ_svi~>c1}aO7TKhyON699R?csqTlSsz&dqi0+ogX}({P2dd-Cz5o)^?S zeD13HTAR;r!|d=|T4|R)3r_K|4yhbGf9L;H6Hcth46DF560hxD7*8~GH&kK&ugb8K z;Cg3U{!75i{igj#?(7{!3|$zP)(Y}3d@_=s{r}_9^7vE(fB2|n{T7-beXpl@{CAh{ zo%j}rXD!1U+d%G!|1yChe5ascz;8jfZ%wCPzwEG=ti{Gn2VXV6o7~TpK5Q`#`xEE> zZFq!wc}dbhLLz?S(+_T98|HFNM0?>2^~U;(X)RsFJHLMkRflqefm0AS-!mo75%=rz zJ1_Y(g-P8T^e^Tc4vj{y-M=-owLDukG6x>(?)}#N(L*5ce%u&&Be>u`F>zLGY6X%Y zxX{uykf9?toJSGRaT3?879C$PT(^i|=PhyHR63!bR}8ZL8JnC*-z*hKs6jJheyB*(?ULN&Hs>Mjp5dZ<#+tG_v-Fi5l$z2e#zU!0#=0%k7qz) zCrIZ)WWPXU?)cVtSiDJRgi) zhVa~KHi$6%93KU1#9BO-G2|aq2e{j(P8oxW?pboJ(3^j6@*k>dSr`p%v~3?&X}o%O zCnM1RLZrw7&zweaYHeV#hN2`bSiNJdioUF9yUclqKwFVcLX3z$*RC-WNxPM55Y(A@z)DbJtCroz2E%vcAL=@|3D8hC|Bk#lg?Sm$GWsRpzL!GGS z;x*T;KE3OvmYryci77S7+uu_S;EICsrp5Zzf*$iejuvVyTD5wyy?(=Ib9@?hTcAT~ zTX==I`DGdP6nNA#7I;tSk{@(9V8})7;4g0H<;lsV;HtHmwPNGiUPv)}P%O34&nKcH z@zTiY(P;byxAA4jc97uC-Q!o>d<9cRn1xXjSF692a*f?vSzWo5wu1rWpiCOR%B$Di ziIdzAUCtikb=BsLnv~-0HD2ctOk7nrbMY4=;JMjei><-=#o(SVA#1XS97&?v-?BQ- zz1t<u!q+u7g>WVaGKm^T+^+JI)>tt!n_62YkVrD{O>Qc#IQ_C1oaLjL#}U^IDIT{*Zu7&Y17>wn zh3=x~1sB$*`|nIkZ5Ji{iaNQLY4r_vvtVNb>pPONnqrBpNL(fjo2Zwv(cf$GFGer$ z8_wDPSqrf5nsfVa$zFd

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Initialise the overlap matrix stored in int_store_t into a mat_t object + call init_mat_t(sys, int_store%ovlp, ovlp) + + ! S^(-1/2) = C * L^(-1/2) * C^(T) + call orthogonalise(ovlp) + call build_ortmat(ovlp, ortmat) + + ! Initial guess Fock matrix + ! F_0 = S^T(-1/2) * H_core * S^(-1/2) + fock = 0.0_p + fock = matmul(int_store%core_hamil, ortmat) + fock = matmul(transpose(ortmat), fock) + + call init_mat_ + + + end subroutine do_hartree_fock + + + subroutine orthogonalise(mat) + ! For a symmetric matrix A we produce + ! A = CLC^(-1) + ! With L and C stored in a mat_t data structure + + use linalg + use error_handling + + type(mat_t), intent(inout) :: mat + + integer :: ierr + + call eigs(mat, ierr) + if (ierr /= 0) call error('hf::orthogonalise', 'Orthogonalisation failed!') + + end subroutine orthogonalise + + subroutine init_mat_t(sys, matrix, mat) + use read_in_integrals + use linalg, only: mat_t + use system + + type(system_t), intent(in) :: sys + real(p), intent(in) :: matrix(:,:) + type(mat_t), intent(out) :: mat + + mat%N = sys%nbasis + allocate(mat%A(mat%N, mat%N)) + mat%A(:,:) = matrix(:,:) + allocate(mat%W(sys%nbasis)) + + end subroutine init_mat_t + + subroutine build_ortmat(ovlp, ortmat) + + use linalg, only: mat_t + + type(mat_t), intent(in) :: ovlp + real(p), allocatable, intent(out) :: ortmat(:,:) + + real(p), allocatable :: tmpmat(:,:) + + integer :: i + + associate(n=>ovlp%N, diag=>ovlp%W) + allocate(ortmat(n, n), source = 0.0_p) + allocate(tmpmat(n, n), source = 0.0_p) + do i = 1, n + ortmat(i,i) = 1/sqrt(diag(i)) + end do + end associate + + tmpmat = matmul(ortmat, transpose(ovlp%A)) + ortmat = matmul(ovlp%A, tmpmat) + + deallocate(tmpmat) + + end subroutine build_ortmat + +end module hf diff --git a/Project#03/fortran/src/linalg.f90 b/src/linalg.f90 similarity index 100% rename from Project#03/fortran/src/linalg.f90 rename to src/linalg.f90 diff --git a/Project#03/fortran/src/main.F90 b/src/main.F90 similarity index 100% rename from Project#03/fortran/src/main.F90 rename to src/main.F90 diff --git a/Project#03/fortran/src/read_in_integrals.f90 b/src/read_in_integrals.f90 similarity index 96% rename from Project#03/fortran/src/read_in_integrals.f90 rename to src/read_in_integrals.f90 index b360475..e58ca55 100644 --- a/Project#03/fortran/src/read_in_integrals.f90 +++ b/src/read_in_integrals.f90 @@ -22,7 +22,7 @@ subroutine read_integrals_in(sys, int_store) type(int_store_t), intent(inout) :: int_store type(system_t), intent(inout) :: sys - character(10) :: enuc_f, ovlp_f, ke_f, ele_nuc_f, eri_f + character(20) :: enuc_f, ovlp_f, ke_f, ele_nuc_f, eri_f integer :: i, j, iunit, ir, natoms, ios, nbasis, ibasis, jbasis, abasis, bbasis real(p) :: intgrl @@ -35,11 +35,11 @@ subroutine read_integrals_in(sys, int_store) nbasis = 0 ! Hard-coded filenames - enuc_f = 'enuc.dat' - ovlp_f = 's.dat' - ke_f = 't.dat' - ele_nuc_f = 'v.dat' - eri_f = 'eri.dat' + enuc_f = 'dat/enuc.dat' + ovlp_f = 'dat/s.dat' + ke_f = 'dat/t.dat' + ele_nuc_f = 'dat/v.dat' + eri_f = 'dat/eri.dat' !########### Nuclear repulsion ############ write(iunit, *) 'Reading nuclear repulsion...' diff --git a/Project#03/fortran/src/system.f90 b/src/system.f90 similarity index 100% rename from Project#03/fortran/src/system.f90 rename to src/system.f90 From e7c322a1019bce966faba1d0cc6cee01665ca5f7 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 15 Dec 2021 14:54:20 +0000 Subject: [PATCH 04/71] Update README.md --- README.md | 67 +++---------------------------------------------------- 1 file changed, 3 insertions(+), 64 deletions(-) diff --git a/README.md b/README.md index d2ad75d..a344cf7 100644 --- a/README.md +++ b/README.md @@ -1,64 +1,3 @@ -# C++ Programming Tutorial in Chemistry -This tutorial is intended to touch on many, but certainly not all, of the fundamentals of C++ programming with an emphasis on quantum chemistry. Although I hope this section will get you started, it is not a substitute for a more complete reference manual. For more C++ language details, you may find the standard text by Josuttis [buy it](http://www.amazon.com/C-Standard-Library-Tutorial-Reference/dp/0201379260) useful or, for VT users, get it [on-line from the campus library](http://proquest.safaribooksonline.com/0201379260) or a decent on-line tutorial such as [this one](http://www.cplusplus.com/doc/tutorial/) or [this one](http://www.cprogramming.com/tutorial.html). - -If you are new to programming, one way to approach this tutorial is to read through "The Fundamentals" list on the [wiki](https://github.com/CrawfordGroup/ProgrammingProjects/wiki) first, then proceed with Project #1, using the earlier material as a reference. If you are already experienced with programming, you may be able to start immediately with Project #1. If you already have experience with electronic structure theory programs, then you may be ready for the Hartee-Fock programming project or even more advanced topics. - -# Getting Started -This repository is organized into several projects, each with its own directory. -In each one you will find a `README.md` file like this one with instructions, -and output for you to check your implementation against. -These projects will also require some input files that will be discussed -in each project as they become relevant. -These input files can be found in the `inputs` directory. -Within `input` there are directories for several different molecule/basis-set -combinations where you will find integrals, molecular geometries and other files to use as input to your programs. - -The wiki for this repository has some discussion of useful topics. -Reading over the topics in the [wiki](addlink) is a good way to familiarize yourself with concepts you will use to complete these projects. -The Fundamentals list below has links to pages within the wiki. - -To begin work on the projects you can create a `clone` of this repository. -First navigate to the directory where you would like to keep your programming projects. Then create the clone by this command -```shell -git clone git@github.com:CrawfordGroup/ProgrammingProjects.git -``` -Now you should see a directory called `ProgrammingProjects` inside you will find all of the files that you can see on github. - -# The Fundamentals - - [An Initial Example](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/An-Initial-Example) - - [What is a "Compilation"](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/What-is-a-%22Compilation%22%3F) - - [Code Comments](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Code-Comments) - - [Data Types and Variables](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Data-Types-and-Variables) - - [Operators](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Operators) - - [Control Statements](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Control-Statements) - - [Input/Output](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Input-Output) - - [Functions](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Functions) - - [Variable Scope and Reference Types](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Variable-Scope-and-Reference-Types) - - [Memory Allocation](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Memory-Allocation) - - [Classes and Objects](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Classes-and-Objects) - - [Overloading and Templates](https://github.com/CrawfordGroup/ProgrammingProjects/wiki/Overloading-and-Templates) - -# Quantum Chemistry Programming Projects - - [Project #1](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2301): Molecular Geometry/rotational constant analysis - - [Project #2](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2302): Harmonic Vibrational analysis - - [Project #3](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2303): The Hartree-Fock self-consistent field (SCF) procedure. - - [Project #4](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2304): The second-order Moller-Plesset perturbation (MP2) energy. - - [Project #5](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2305): The coupled cluster singles and doubles (CCSD) energy. - - [Project #6](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2306): A perturbative triples correction to CCSD [CCSD(T)]. - - [Project #7](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2307): Connecting your code to PSI4. - - [Project #8](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2308): DIIS extrapolation for the SCF procedure. - - [Project #9](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2309): Using symmetry in the SCF procedure. - - [Project #10](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2310): DIIS extrapolation for solving the CC amplitude equations. - - [Project #11](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2311): An "out of core" SCF procedure. - - [Project #12](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2312): Excited Electronic States: CIS and TDHF/RPA - - [Project #13](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2313): the Davidson-Liu Algorithm: CIS - - [Project #14](https://github.com/CrawfordGroup/ProgrammingProjects/tree/master/Project%2314): Excited Electronic States: EOM-CCSD (*In Preparation*) - -# Possible Future Projects - - Some Future Projects - - SCF Analytic Energy Gradients - - MP2 Analytic Energy Gradients - - Integral-direct SCF - - Response properties: Hartree-Fock dipole-polarizabilities - - Response properties: CCSD dipole-polarizabilities - - Local MP2 +# A Fortran Electronic Structure Programme (AFESP) +This project is based on Crawford Group's excellent C++ Programming Tutorial in Chemistry [tutorial](https://github.com/CrawfordGroup/ProgrammingProjects), but written in Fortran. +The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T) with support for multicore processors (modern CPUs, GPUs). From 141ce3d1be03b935a42a0d4efcaf47258e09d774 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 15 Dec 2021 14:57:58 +0000 Subject: [PATCH 05/71] Update README.md --- README.md | 2 +- 1 file changed, 1 insertion(+), 1 deletion(-) diff --git a/README.md b/README.md index a344cf7..3c6f703 100644 --- a/README.md +++ b/README.md @@ -1,3 +1,3 @@ # A Fortran Electronic Structure Programme (AFESP) -This project is based on Crawford Group's excellent C++ Programming Tutorial in Chemistry [tutorial](https://github.com/CrawfordGroup/ProgrammingProjects), but written in Fortran. +This project is based on Crawford Group's excellent [C++ Programming Tutorial in Chemistry](https://github.com/CrawfordGroup/ProgrammingProjects), but written in Fortran. The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T) with support for multicore processors (modern CPUs, GPUs). From 6aa6d46bc94b588c0e5d64e57cbd5e81f0c76ea6 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 15 Dec 2021 14:59:45 +0000 Subject: [PATCH 06/71] Update README.md --- README.md | 4 ++-- 1 file changed, 2 insertions(+), 2 deletions(-) diff --git a/README.md b/README.md index 3c6f703..138c9bd 100644 --- a/README.md +++ b/README.md @@ -1,3 +1,3 @@ # A Fortran Electronic Structure Programme (AFESP) -This project is based on Crawford Group's excellent [C++ Programming Tutorial in Chemistry](https://github.com/CrawfordGroup/ProgrammingProjects), but written in Fortran. -The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T) with support for multicore processors (modern CPUs, GPUs). +This project is based on the Crawford Group's excellent [C++ Programming Tutorial in Chemistry](https://github.com/CrawfordGroup/ProgrammingProjects), but written in Fortran. +The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as per the original tutorial, but with additional support for multicore processors (modern CPUs, GPUs). From c06b01830d5716f09bc7d45d211cfcd7f91e90c3 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 15 Dec 2021 22:24:53 +0000 Subject: [PATCH 07/71] Working initial density --- .gitignore | 1 + make.sh | 2 +- src/hf.f90 | 62 ++++++++++++++++++++++++++++++++++++------------------ 3 files changed, 43 insertions(+), 22 deletions(-) diff --git a/.gitignore b/.gitignore index a1b035d..1538ce2 100644 --- a/.gitignore +++ b/.gitignore @@ -4,3 +4,4 @@ *.o build/ original_projects/ +els.x diff --git a/make.sh b/make.sh index 01c0601..f9e846e 100644 --- a/make.sh +++ b/make.sh @@ -15,7 +15,7 @@ if [ $n_flag -eq 1 ] then rm -r build mkdir build; cd $_ - cmake .. + cmake .. -DCMAKE_BUILD_TYPE=Debug make cp els.x .. cd .. diff --git a/src/hf.f90 b/src/hf.f90 index 4eb6a22..355d0d4 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -13,7 +13,7 @@ subroutine do_hartree_fock(sys, int_store) type(int_store_t), intent(in) :: int_store type(system_t), intent(in) :: sys - type(mat_t) :: ovlp + type(mat_t) :: ovlp, fockmat real(p) :: ortmat(sys%nbasis,sys%nbasis) real(p) :: fock(sys%nbasis,sys%nbasis) real(p) :: coeff(sys%nbasis,sys%nbasis) @@ -21,10 +21,10 @@ subroutine do_hartree_fock(sys, int_store) real(p) :: tmpmat(sys%nbasis,sys%nbasis) ! Initialise the overlap matrix stored in int_store_t into a mat_t object - call init_mat_t(sys, int_store%ovlp, ovlp) + call init_mat_t(int_store%ovlp, ovlp) ! S^(-1/2) = C * L^(-1/2) * C^(T) - call orthogonalise(ovlp) + call diagonalise(ovlp) call build_ortmat(ovlp, ortmat) ! Initial guess Fock matrix @@ -33,15 +33,24 @@ subroutine do_hartree_fock(sys, int_store) fock = matmul(int_store%core_hamil, ortmat) fock = matmul(transpose(ortmat), fock) - call init_mat_ + call init_mat_t(fock, fockmat) + call diagonalise(fockmat) + ! Transform coefficient into AO basis + fockmat%A = matmul(ortmat, fockmat%A) + + ! Build initial density + ! [TODO]: this is just hard-coded for now for water, URGENT: add geom_read_in + call build_density(fockmat%A, density, 5) + + print*, density end subroutine do_hartree_fock - subroutine orthogonalise(mat) + subroutine diagonalise(mat) ! For a symmetric matrix A we produce - ! A = CLC^(-1) + ! A = C * L * C^T ! With L and C stored in a mat_t data structure use linalg @@ -54,21 +63,22 @@ subroutine orthogonalise(mat) call eigs(mat, ierr) if (ierr /= 0) call error('hf::orthogonalise', 'Orthogonalisation failed!') - end subroutine orthogonalise + end subroutine diagonalise - subroutine init_mat_t(sys, matrix, mat) + subroutine init_mat_t(matrix, mat) use read_in_integrals use linalg, only: mat_t use system - type(system_t), intent(in) :: sys real(p), intent(in) :: matrix(:,:) type(mat_t), intent(out) :: mat - mat%N = sys%nbasis - allocate(mat%A(mat%N, mat%N)) - mat%A(:,:) = matrix(:,:) - allocate(mat%W(sys%nbasis)) + associate(N=>size(matrix, dim=1)) + mat%N = N + allocate(mat%A(N,N)) + mat%A(:,:) = matrix(:,:) + allocate(mat%W(N)) + end associate end subroutine init_mat_t @@ -77,16 +87,17 @@ subroutine build_ortmat(ovlp, ortmat) use linalg, only: mat_t type(mat_t), intent(in) :: ovlp - real(p), allocatable, intent(out) :: ortmat(:,:) + real(p), intent(out) :: ortmat(:,:) - real(p), allocatable :: tmpmat(:,:) + real(p) :: tmpmat(size(ortmat, dim=1), size(ortmat, dim=1)) integer :: i - associate(n=>ovlp%N, diag=>ovlp%W) - allocate(ortmat(n, n), source = 0.0_p) - allocate(tmpmat(n, n), source = 0.0_p) - do i = 1, n + tmpmat(:,:) = 0.0_p + ortmat(:,:) = 0.0_p + + associate(diag=>ovlp%W) + do i = 1, size(ortmat, dim=1) ortmat(i,i) = 1/sqrt(diag(i)) end do end associate @@ -94,8 +105,17 @@ subroutine build_ortmat(ovlp, ortmat) tmpmat = matmul(ortmat, transpose(ovlp%A)) ortmat = matmul(ovlp%A, tmpmat) - deallocate(tmpmat) - end subroutine build_ortmat + + subroutine build_density(coeff, density, nocc) + real(p), intent(in) :: coeff(:,:) + integer, intent(in) :: nocc + real(p), intent(out) :: density(:,:) + + density = matmul(coeff(:, 1:nocc), transpose(coeff(:, 1:nocc))) + + end subroutine build_density + + end module hf From c15a26e91b56955ec617b03a7328d2f4124583d9 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Thu, 16 Dec 2021 16:03:05 +0000 Subject: [PATCH 08/71] Working HF --- src/hf.f90 | 103 +++++++++++++++++++++++++++++++++++++++++-------- src/linalg.f90 | 4 +- src/system.f90 | 6 +++ 3 files changed, 95 insertions(+), 18 deletions(-) diff --git a/src/hf.f90 b/src/hf.f90 index 355d0d4..47e7045 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -20,33 +20,45 @@ subroutine do_hartree_fock(sys, int_store) real(p) :: density(sys%nbasis,sys%nbasis) real(p) :: tmpmat(sys%nbasis,sys%nbasis) + type(state_t) :: st + integer :: iter, maxiter + + maxiter = 50 + + ! Build the orthogonalisation matrix S^-1/2 + ! Initialise the overlap matrix stored in int_store_t into a mat_t object call init_mat_t(int_store%ovlp, ovlp) + ovlp%ao_ort = ovlp%ao ! S^(-1/2) = C * L^(-1/2) * C^(T) call diagonalise(ovlp) call build_ortmat(ovlp, ortmat) - ! Initial guess Fock matrix - ! F_0 = S^T(-1/2) * H_core * S^(-1/2) - fock = 0.0_p - fock = matmul(int_store%core_hamil, ortmat) - fock = matmul(transpose(ortmat), fock) + call deallocate_mat_t(ovlp) - call init_mat_t(fock, fockmat) - call diagonalise(fockmat) + ! Initial guess Fock matrix is H_core + ! F'_0 = S^T(-1/2) * F * S^(-1/2) + call init_mat_t(int_store%core_hamil, fockmat) - ! Transform coefficient into AO basis - fockmat%A = matmul(ortmat, fockmat%A) + do iter = 1, maxiter + fockmat%ao_ort = matmul(transpose(ortmat), matmul(fockmat%ao, ortmat)) - ! Build initial density - ! [TODO]: this is just hard-coded for now for water, URGENT: add geom_read_in - call build_density(fockmat%A, density, 5) + call diagonalise(fockmat) - print*, density + ! Transform coefficient into nonorthogonal AO basis + fockmat%A = transpose(matmul(ortmat, fockmat%A)) - end subroutine do_hartree_fock + ! [TODO]: this is just hard-coded for now for water, URGENT: add geom_read_in + call build_density(fockmat%A, density, 5) + call scf_energy(density, fockmat%ao, st, int_store) + print*, st%energy + + call build_fock(sys, density, fockmat%ao, int_store) + end do + + end subroutine do_hartree_fock subroutine diagonalise(mat) ! For a symmetric matrix A we produce @@ -60,8 +72,10 @@ subroutine diagonalise(mat) integer :: ierr + ! Overwrite the previous coeff matrix + mat%A = mat%ao_ort call eigs(mat, ierr) - if (ierr /= 0) call error('hf::orthogonalise', 'Orthogonalisation failed!') + if (ierr /= 0) call error('hf::diagonalise', 'Diagonalisation failed!') end subroutine diagonalise @@ -75,13 +89,27 @@ subroutine init_mat_t(matrix, mat) associate(N=>size(matrix, dim=1)) mat%N = N + allocate(mat%ao(N,N)) allocate(mat%A(N,N)) - mat%A(:,:) = matrix(:,:) + allocate(mat%ao_ort(N,N)) + mat%ao(:,:) = matrix(:,:) allocate(mat%W(N)) end associate end subroutine init_mat_t + subroutine deallocate_mat_t(mat) + use linalg, only: mat_t + + type(mat_t), intent(inout) :: mat + + mat%N = 0 + deallocate(mat%ao) + deallocate(mat%ao_ort) + deallocate(mat%A) + deallocate(mat%W) + end subroutine deallocate_mat_t + subroutine build_ortmat(ovlp, ortmat) use linalg, only: mat_t @@ -112,10 +140,51 @@ subroutine build_density(coeff, density, nocc) integer, intent(in) :: nocc real(p), intent(out) :: density(:,:) - density = matmul(coeff(:, 1:nocc), transpose(coeff(:, 1:nocc))) + density = matmul(transpose(coeff(1:nocc, :)), coeff(1:nocc, :)) end subroutine build_density + subroutine scf_energy(density, fock, st, int_store) + + use system, only: state_t + use read_in_integrals, only: int_store_t + real(p), intent(in) :: density(:,:) + real(p), intent(in) :: fock(:,:) + type(int_store_t), intent(in) :: int_store + type(state_t), intent(inout) :: st + + st%energy_old = st%energy + + st%energy = sum(density * (int_store%core_hamil + fock)) + + end subroutine scf_energy + subroutine build_fock(sys, density, fock, int_store) + + use read_in_integrals, only: int_store_t, eri_ind + use system, only: system_t + + real(p), intent(in) :: density(:,:) + type(int_store_t), intent(in) :: int_store + type(system_t), intent(in) :: sys + real(p), intent(out) :: fock(:,:) + + integer :: i, j, k, l + + associate(eri=>int_store%eri) + do j = 1, sys%nbasis + do i = 1, sys%nbasis + fock(i,j) = int_store%core_hamil(i,j) + do l = 1, sys%nbasis + do k = 1, sys%nbasis + fock(i,j) = fock(i,j) + density(k,l) * (2*eri(eri_ind(i,j,k,l)) - eri(eri_ind(i,k,j,l))) + end do + end do + end do + end do + end associate + + end subroutine build_fock + end module hf diff --git a/src/linalg.f90 b/src/linalg.f90 index e76127e..aea55bc 100644 --- a/src/linalg.f90 +++ b/src/linalg.f90 @@ -6,7 +6,9 @@ module linalg type mat_t ! A structure that holds the original matrix, the eigenvalues and the eigenvalue matrix integer :: N = -1 ! Dimension - real(p), allocatable :: A(:,:) ! Original/eigenvector matrix + real(p), allocatable :: ao(:,:) ! AO basis matrix + real(p), allocatable :: ao_ort(:,:) ! Orthonormal AO basis + real(p), allocatable :: A(:,:) ! eigenvector matrix after diagonalisation real(p), allocatable :: W(:) ! Eigenvalues end type mat_t diff --git a/src/system.f90 b/src/system.f90 index c68bec3..a09cf23 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -7,4 +7,10 @@ module system integer :: nbasis = 0 end type system_t + type state_t + integer :: iter = 0 + real(p) :: energy = 0.0_p + real(p) :: energy_old = 0.0_p + end type state_t + end module system \ No newline at end of file From 76244fe9c2b6c4d3b24c55bb47bd6553be74c10e Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Fri, 17 Dec 2021 10:55:39 +0000 Subject: [PATCH 09/71] Add read-in functionalities --- src/geometry.f90 | 90 +++++++++++++++++++++++++++++++++++++++ src/main.F90 | 10 +++-- src/read_in_integrals.f90 | 8 ++-- src/system.f90 | 5 +++ 4 files changed, 106 insertions(+), 7 deletions(-) create mode 100644 src/geometry.f90 diff --git a/src/geometry.f90 b/src/geometry.f90 new file mode 100644 index 0000000..417fd83 --- /dev/null +++ b/src/geometry.f90 @@ -0,0 +1,90 @@ +module geometry + use const + + implicit none + + contains + + subroutine read_geometry_in(sys, int_store) + ! Read in geometry data supplied in a file + use system, only: system_t + use read_in_integrals, only: int_store_t + + type(system_t), intent(inout) :: sys + type(int_store_t), intent(inout) :: int_store + + integer :: i, iunit, ir + real(p) :: charge + + ! stdout unit is 6 + iunit = 6 + + ! newunit chooses an unused file handle, 'old' means existing file + open(newunit=ir, file='dat/geom.dat', status='old', form='formatted') + read(ir, *) sys%natoms + + ! Lazy allocation! + ! [TODO] make check_allocate subroutine + allocate(sys%charges(sys%natoms)) + allocate(sys%coords(3,sys%natoms)) + + do i = 1, sys%natoms + read(ir, *) charge, sys%coords(:,i) + sys%charges(i) = int(charge) + end do + + close(ir) + + sys%nel = sum(sys%charges) + + call get_e_nuc(sys, int_store%e_nuc) + + + end subroutine read_geometry_in + + subroutine get_bond_lengths(coords, bondlengths) + real(p), intent(in) :: coords(:,:) + real(p), allocatable, intent(out) :: bondlengths(:,:) + + integer :: i, j + + ! Negligible memeory cost to store the full matrix rather than the lower triangular + associate(natoms=>size(coords, dim=1)) + allocate(bondlengths(natoms, natoms), source=0.0_p) + + do i = 1, natoms-1 + do j = i+1, natoms + ! Diagonals set to 0.0 in allocation + bondlengths(j, i) = norm2(coords(:,i)-coords(:,j)) + bondlengths(i, j) = bondlengths(j, i) + end do + end do + end associate + end subroutine get_bond_lengths + + subroutine get_e_nuc(sys, e_nuc) + use system, only: system_t + + type(system_t), intent(in) :: sys + real(p), intent(out) :: e_nuc + real(p), allocatable :: bondlengths(:,:) + + integer :: i, j + + call get_bond_lengths(sys%coords, bondlengths) + + e_nuc = 0.0_p + do j = 2, size(sys%charges) + do i = 1, j-1 + e_nuc = e_nuc + sys%charges(i)*sys%charges(j)/bondlengths(i,j) + end do + end do + + ! Explicitly deallocate instead of using scoping rules.. is it necessary? + deallocate(bondlengths) + + end subroutine get_e_nuc + + + +end module geometry diff --git a/src/main.F90 b/src/main.F90 index 70cd164..b10873f 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -1,9 +1,10 @@ program main use const - use read_in_integrals - use system - use hf + use read_in_integrals, only: read_integrals_in, print_int_info, int_store_t + use system, only: system_t + use hf, only: do_hartree_fock + use geometry, only: read_geometry_in implicit none @@ -16,7 +17,10 @@ program main write(iunit, *) 'Electronic Structure Programme' + call read_integrals_in(sys, int_store) + call read_geometry_in(sys, int_store) + call print_int_info(sys, int_store) call do_hartree_fock(sys, int_store) diff --git a/src/read_in_integrals.f90 b/src/read_in_integrals.f90 index e58ca55..b6d7d15 100644 --- a/src/read_in_integrals.f90 +++ b/src/read_in_integrals.f90 @@ -42,10 +42,10 @@ subroutine read_integrals_in(sys, int_store) eri_f = 'dat/eri.dat' !########### Nuclear repulsion ############ - write(iunit, *) 'Reading nuclear repulsion...' - open(newunit=ir, file=enuc_f, status='old', form='formatted') - read(ir, *) int_store%e_nuc - close(ir) + !write(iunit, *) 'Reading nuclear repulsion...' + !open(newunit=ir, file=enuc_f, status='old', form='formatted') + !read(ir, *) int_store%e_nuc + !close(ir) !########### Get basis info ############### write(iunit, *) 'Getting number of basis functions...' diff --git a/src/system.f90 b/src/system.f90 index a09cf23..86b5c0f 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -4,7 +4,12 @@ module system implicit none type system_t + integer :: nel = 0 integer :: nbasis = 0 + integer :: natoms = 0 + + integer, allocatable :: charges(:) + real(p), allocatable :: coords(:,:) end type system_t type state_t From c3edcb04d33767c26c3adb55928152a250835283 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Fri, 17 Dec 2021 11:48:04 +0000 Subject: [PATCH 10/71] Add convergence checking and more printing --- src/hf.f90 | 34 +++++++++++++++++++++++++++------- src/main.F90 | 8 +++++--- src/read_in_integrals.f90 | 22 +++++++++++----------- src/system.f90 | 4 +++- 4 files changed, 46 insertions(+), 22 deletions(-) diff --git a/src/hf.f90 b/src/hf.f90 index 47e7045..1b6e7a4 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -21,12 +21,19 @@ subroutine do_hartree_fock(sys, int_store) real(p) :: tmpmat(sys%nbasis,sys%nbasis) type(state_t) :: st - integer :: iter, maxiter + integer :: iter, maxiter, iunit + logical :: conv = .false. + iunit = 6 maxiter = 50 + write(iunit, '(1X, 12("-"))') + write(iunit, '(1X, A)') 'Hartree-Fock' + write(iunit, '(1X, 12("-"))') - ! Build the orthogonalisation matrix S^-1/2 + allocate(st%density(sys%nbasis,sys%nbasis), source=0.0_p) + allocate(st%density_old(sys%nbasis,sys%nbasis), source=0.0_p) + ! Build the orthogonalisation matrix S^-1/2 ! Initialise the overlap matrix stored in int_store_t into a mat_t object call init_mat_t(int_store%ovlp, ovlp) ovlp%ao_ort = ovlp%ao @@ -52,12 +59,20 @@ subroutine do_hartree_fock(sys, int_store) ! [TODO]: this is just hard-coded for now for water, URGENT: add geom_read_in call build_density(fockmat%A, density, 5) - call scf_energy(density, fockmat%ao, st, int_store) - print*, st%energy + call update_scf_energy(density, fockmat%ao, st, int_store, conv) + if (conv) then + write(iunit, '(1X, A)') 'Convergence reached within tolerance.' + write(iunit, '(1X, A, 1X, F15.8)') 'Final SCF Energy (Hartree):', st%energy + exit + else + write(iunit, '(1X, A, 1X, I0, F15.8)') 'Iteration', iter, st%energy + end if call build_fock(sys, density, fockmat%ao, int_store) end do + + end subroutine do_hartree_fock subroutine diagonalise(mat) @@ -144,7 +159,7 @@ subroutine build_density(coeff, density, nocc) end subroutine build_density - subroutine scf_energy(density, fock, st, int_store) + subroutine update_scf_energy(density, fock, st, int_store, conv) use system, only: state_t use read_in_integrals, only: int_store_t @@ -153,12 +168,17 @@ subroutine scf_energy(density, fock, st, int_store) real(p), intent(in) :: fock(:,:) type(int_store_t), intent(in) :: int_store type(state_t), intent(inout) :: st + logical, intent(inout) :: conv + st%density_old = st%density + st%density = density + st%energy_old = st%energy - st%energy = sum(density * (int_store%core_hamil + fock)) - end subroutine scf_energy + if (sqrt(sum((density-st%density_old)**2)) < 1e5*depsilon .and. abs(st%energy-st%energy_old) < 1e5*depsilon) conv = .true. + + end subroutine update_scf_energy subroutine build_fock(sys, density, fock, int_store) diff --git a/src/main.F90 b/src/main.F90 index b10873f..44a3841 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -1,7 +1,7 @@ program main use const - use read_in_integrals, only: read_integrals_in, print_int_info, int_store_t + use read_in_integrals, only: read_integrals_in, print_sys_info, int_store_t use system, only: system_t use hf, only: do_hartree_fock use geometry, only: read_geometry_in @@ -15,13 +15,15 @@ program main ! write to stdout iunit = 6 - write(iunit, *) 'Electronic Structure Programme' + write(iunit, '(1X, 64("="))') + write(iunit, '(1X, A)') 'A Fortran Electronic Structure Programme (AFESP)' + write(iunit, '(1X, 64("="))') call read_integrals_in(sys, int_store) call read_geometry_in(sys, int_store) - call print_int_info(sys, int_store) + call print_sys_info(sys, int_store) call do_hartree_fock(sys, int_store) diff --git a/src/read_in_integrals.f90 b/src/read_in_integrals.f90 index b6d7d15..710c3de 100644 --- a/src/read_in_integrals.f90 +++ b/src/read_in_integrals.f90 @@ -41,11 +41,10 @@ subroutine read_integrals_in(sys, int_store) ele_nuc_f = 'dat/v.dat' eri_f = 'dat/eri.dat' - !########### Nuclear repulsion ############ - !write(iunit, *) 'Reading nuclear repulsion...' - !open(newunit=ir, file=enuc_f, status='old', form='formatted') - !read(ir, *) int_store%e_nuc - !close(ir) + write(iunit, '(1X, 16("-"))') + write(iunit, '(1X, A)') 'Integral read-in' + write(iunit, '(1X, 16("-"))') + !########### Get basis info ############### write(iunit, *) 'Getting number of basis functions...' @@ -114,7 +113,7 @@ subroutine read_integrals_in(sys, int_store) int_store%core_hamil = int_store%ke + int_store%ele_nuc !######### ERI / Two-body integrals ######## - write(iunit, *) 'Reading two-body integrals' + write(iunit, *) 'Reading two-body integrals...' open(newunit=ir, file=eri_f, status='old', form='formatted') do @@ -175,7 +174,7 @@ elemental function eri_ind(i, j, a, b) result(ind) end if end function eri_ind - subroutine print_int_info(sys, int_store) + subroutine print_sys_info(sys, int_store) use system type(system_t), intent(in) :: sys @@ -184,12 +183,13 @@ subroutine print_int_info(sys, int_store) integer :: iunit = 6 integer :: i - write(iunit, '(1X, 64("="))') - write(iunit, '(1X, A)') 'Integral information' - write(iunit, '(1X, 64("="))') + write(iunit, '(1X, 20("-"))') + write(iunit, '(1X, A)') 'System information' + write(iunit, '(1X, 20("-"))') + write(iunit, '(1X, A, 1X, I0)') 'Number of electrons:', sys%nel write(iunit, '(1X, A, 1X, I0)') 'Number of basis functions:', sys%nbasis write(iunit, '(1X, A, 1X, ES15.8)') 'E_nuc:', int_store%e_nuc - end subroutine print_int_info + end subroutine print_sys_info end module read_in_integrals diff --git a/src/system.f90 b/src/system.f90 index 86b5c0f..b8dde9b 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -4,7 +4,7 @@ module system implicit none type system_t - integer :: nel = 0 + integer :: nel = 0 integer :: nbasis = 0 integer :: natoms = 0 @@ -16,6 +16,8 @@ module system integer :: iter = 0 real(p) :: energy = 0.0_p real(p) :: energy_old = 0.0_p + real(p), allocatable :: density(:,:) + real(p), allocatable :: density_old(:,:) end type state_t end module system \ No newline at end of file From aba88e0481a88a7ee0d5a2aa01c0f7293b766732 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Fri, 17 Dec 2021 15:29:26 +0000 Subject: [PATCH 11/71] Add timing routines --- src/hf.f90 | 9 ++++++--- src/main.F90 | 19 ++++++++++++++++--- 2 files changed, 22 insertions(+), 6 deletions(-) diff --git a/src/hf.f90 b/src/hf.f90 index 1b6e7a4..9a1eb8b 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -21,7 +21,7 @@ subroutine do_hartree_fock(sys, int_store) real(p) :: tmpmat(sys%nbasis,sys%nbasis) type(state_t) :: st - integer :: iter, maxiter, iunit + integer :: iter, maxiter, iunit, i logical :: conv = .false. iunit = 6 @@ -63,6 +63,10 @@ subroutine do_hartree_fock(sys, int_store) if (conv) then write(iunit, '(1X, A)') 'Convergence reached within tolerance.' write(iunit, '(1X, A, 1X, F15.8)') 'Final SCF Energy (Hartree):', st%energy + write(iunit, '(1X, A)') 'Orbital energies (Hartree):' + do i = size(fockmat%W), 1, -1 + write(iunit, '(1X, I0, 1X, F15.8)') i, fockmat%W(i) + end do exit else write(iunit, '(1X, A, 1X, I0, F15.8)') 'Iteration', iter, st%energy @@ -71,8 +75,6 @@ subroutine do_hartree_fock(sys, int_store) call build_fock(sys, density, fockmat%ao, int_store) end do - - end subroutine do_hartree_fock subroutine diagonalise(mat) @@ -198,6 +200,7 @@ subroutine build_fock(sys, density, fock, int_store) fock(i,j) = int_store%core_hamil(i,j) do l = 1, sys%nbasis do k = 1, sys%nbasis + ! [TODO]: This step can be sped up with pre-computed lookup arrays fock(i,j) = fock(i,j) + density(k,l) * (2*eri(eri_ind(i,j,k,l)) - eri(eri_ind(i,k,j,l))) end do end do diff --git a/src/main.F90 b/src/main.F90 index 44a3841..07bbd78 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -11,6 +11,8 @@ program main type(int_store_t) :: int_store type(system_t) :: sys integer :: i, iunit + integer(kind=8) :: t0, t1, count_rate, count_max + integer :: date_values(8) ! write to stdout iunit = 6 @@ -19,13 +21,24 @@ program main write(iunit, '(1X, A)') 'A Fortran Electronic Structure Programme (AFESP)' write(iunit, '(1X, 64("="))') + call date_and_time(VALUES=date_values) + write(iunit, '(1X, A, 1X, I2.2, "/", I2.2, "/", I4.4, 1X, A, 1X, I2.2, 2(":", I2.2))') & + "Started running on", date_values(3:1:-1), "at", date_values(5:7) + + call system_clock(t0, count_rate, count_max) call read_integrals_in(sys, int_store) call read_geometry_in(sys, int_store) - call print_sys_info(sys, int_store) + call system_clock(t1) + if (t1 Date: Sat, 18 Dec 2021 18:54:19 +0000 Subject: [PATCH 12/71] Working MP2 with N^5 loops, further optimisation possible. --- .gitignore | 1 + make.sh | 18 +++- src/hf.f90 | 26 +++-- src/main.F90 | 8 ++ src/mp2.f90 | 214 ++++++++++++++++++++++++++++++++++++++ src/read_in_integrals.f90 | 33 +++--- src/system.f90 | 15 ++- 7 files changed, 286 insertions(+), 29 deletions(-) create mode 100644 src/mp2.f90 diff --git a/.gitignore b/.gitignore index 1538ce2..008635c 100644 --- a/.gitignore +++ b/.gitignore @@ -5,3 +5,4 @@ build/ original_projects/ els.x +dat/ diff --git a/make.sh b/make.sh index f9e846e..38ca011 100644 --- a/make.sh +++ b/make.sh @@ -1,21 +1,33 @@ #!/bin/bash +# -n: Make afresh +# -p: Production + n_flag=0 +p_flag=0 -while getopts 'n' flag +while getopts 'np' flag do case "${flag}" in n) n_flag=1 ;; - *) n_flag=0 + p) p_flag=1 ;; + *) n_flag=0; p_flag=0 exit 1 ;; esac done +if [ $p_flag -ne 1 ] +then + cmakeopt='-DCMAKE_BUILD_TYPE=Debug' +else + cmakeopt='' +fi + if [ $n_flag -eq 1 ] then rm -r build mkdir build; cd $_ - cmake .. -DCMAKE_BUILD_TYPE=Debug + cmake .. ${cmakeopt} make cp els.x .. cd .. diff --git a/src/hf.f90 b/src/hf.f90 index 9a1eb8b..e2217fe 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -11,7 +11,7 @@ subroutine do_hartree_fock(sys, int_store) use linalg type(int_store_t), intent(in) :: int_store - type(system_t), intent(in) :: sys + type(system_t), intent(inout) :: sys type(mat_t) :: ovlp, fockmat real(p) :: ortmat(sys%nbasis,sys%nbasis) @@ -25,7 +25,7 @@ subroutine do_hartree_fock(sys, int_store) logical :: conv = .false. iunit = 6 - maxiter = 50 + maxiter = 100 write(iunit, '(1X, 12("-"))') write(iunit, '(1X, A)') 'Hartree-Fock' write(iunit, '(1X, 12("-"))') @@ -65,16 +65,25 @@ subroutine do_hartree_fock(sys, int_store) write(iunit, '(1X, A, 1X, F15.8)') 'Final SCF Energy (Hartree):', st%energy write(iunit, '(1X, A)') 'Orbital energies (Hartree):' do i = size(fockmat%W), 1, -1 - write(iunit, '(1X, I0, 1X, F15.8)') i, fockmat%W(i) + write(iunit, '(1X, I3, 1X, F15.8)') i, fockmat%W(i) end do + + ! Copied for return / use in MP2 + sys%e_hf = st%energy + allocate(sys%canon_coeff, source=fockmat%A) + allocate(sys%canon_levels, source=fockmat%W) exit else - write(iunit, '(1X, A, 1X, I0, F15.8)') 'Iteration', iter, st%energy + write(iunit, '(1X, A, 1X, I3, F15.8)') 'Iteration', iter, st%energy end if call build_fock(sys, density, fockmat%ao, int_store) end do + if (.not. conv) then + write(iunit, '(1X, A)') 'Convergence not reached, please increase maxiter.' + end if + end subroutine do_hartree_fock subroutine diagonalise(mat) @@ -178,7 +187,7 @@ subroutine update_scf_energy(density, fock, st, int_store, conv) st%energy_old = st%energy st%energy = sum(density * (int_store%core_hamil + fock)) - if (sqrt(sum((density-st%density_old)**2)) < 1e5*depsilon .and. abs(st%energy-st%energy_old) < 1e5*depsilon) conv = .true. + if (sqrt(sum((density-st%density_old)**2)) < 1e-5 .and. abs(st%energy-st%energy_old) < 1e-5) conv = .true. end subroutine update_scf_energy @@ -193,15 +202,20 @@ subroutine build_fock(sys, density, fock, int_store) real(p), intent(out) :: fock(:,:) integer :: i, j, k, l + integer :: ij, kl, ik, jl associate(eri=>int_store%eri) do j = 1, sys%nbasis do i = 1, sys%nbasis fock(i,j) = int_store%core_hamil(i,j) + ij = eri_ind(i,j) do l = 1, sys%nbasis + jl = eri_ind(j,l) do k = 1, sys%nbasis ! [TODO]: This step can be sped up with pre-computed lookup arrays - fock(i,j) = fock(i,j) + density(k,l) * (2*eri(eri_ind(i,j,k,l)) - eri(eri_ind(i,k,j,l))) + kl = eri_ind(k,l) + ik = eri_ind(i,k) + fock(i,j) = fock(i,j) + density(k,l) * (2*eri(eri_ind(ij,kl)) - eri(eri_ind(ik,jl))) end do end do end do diff --git a/src/main.F90 b/src/main.F90 index 07bbd78..fe79bbb 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -5,6 +5,7 @@ program main use system, only: system_t use hf, only: do_hartree_fock use geometry, only: read_geometry_in + use mp2, only: do_mp2 implicit none @@ -40,5 +41,12 @@ program main if (t1sys%canon_coeff,eri=>int_store%eri) + do p = 1, n + do q = 1, p + ! If r>p, rs>pq, and we want rs <= pq + do r = 1, p + if (p==r) then + ! If p==r, then s must be smaller than q for rs <= pq + s_up = q + else + ! Default rules + s_up = r + end if + do s = 1, s_up + pqrs = pqrs + 1 + do i = 1, n + do j = 1, n + ij = eri_ind(i,j) + do k = 1, n + do l = 1, n + kl = eri_ind(k,l) + int_store%eri_mo(pqrs) = int_store%eri_mo(pqrs) & + + C(p,i)*C(q,j)*C(r,k)*C(s,l)*eri(eri_ind(ij,kl)) + end do + end do + end do + end do + end do + end do + end do + end do + end associate + + nocc = sys%nel/2 + associate(e=>sys%canon_levels, eri=>int_store%eri_mo, emp=>sys%e_mp2) + do i = 1, nocc + do j = 1, nocc + do a = nocc+1, n + ia = eri_ind(i,a) + ja = eri_ind(j,a) + do b = nocc+1, n + jb = eri_ind(j,b) + ib = eri_ind(i,b) + emp = emp+(eri(eri_ind(ia,jb))*(2*eri(eri_ind(ia,jb))-eri(eri_ind(ib,ja))))& + / (e(i)+e(j)-e(a)-e(b)) + end do + end do + end do + end do + end associate + print*, sys%e_mp2 + + end subroutine do_mp2_naive + + subroutine do_mp2(sys, int_store) + + use system, only: system_t + use read_in_integrals, only: int_store_t, eri_ind + + type(system_t), intent(inout) :: sys + type(int_store_t), intent(inout) :: int_store + + real(dp), allocatable :: tmp_a(:,:,:,:) + real(dp), allocatable :: tmp_b(:,:,:,:) ! mixed integrals like (ij|rs) + integer :: tmpdim, n, nocc + integer :: i, j, k, l, p, q, r, s, a, b + integer :: kl, ij, pq, rs, pqrs, s_up + integer :: ia, ja, jb, ib + + n = sys%nbasis + tmpdim = n*(n+1)/2 + + ! dp used because 'p' is already a variable here + allocate(tmp_a(n, n, n, n), source=0.0_dp) + allocate(tmp_b(n, n, n, n), source=0.0_dp) + + allocate(int_store%eri_mo, mold=int_store%eri) + + associate(C=>sys%canon_coeff, eri_mo=>int_store%eri_mo, eri=>int_store%eri) + ! (ij|kl) -> (pj|kl) + do k = 1, n + do l = 1, n + kl = eri_ind(k,l) + do j = 1, n + do i = 1, n + ij = eri_ind(i,j) + do p = 1, n + tmp_a(p, j, k, l) = tmp_a(p, j, k, l) + eri(eri_ind(ij,kl))*C(p,i) + end do + end do + end do + end do + end do + + ! (pj|kl) -> (pq|kl) + do k = 1, n + do l = 1, n + kl = eri_ind(k,l) + do p = 1, n + do j = 1, n + do q = 1, n + tmp_b(p,q, k, l) = tmp_b(p,q, k,l) + tmp_a(p, j, k,l)*C(q,j) + end do + end do + end do + end do + end do + + ! (pq|kl) -> (pq|rl) + tmp_a(:,:,:,:) = 0.0_dp + pq = 0 + do p = 1, n + do q = 1, n + pq = eri_ind(p,q) + do k = 1, n + do l = 1, n + kl = eri_ind(k,l) + do r = 1, n + tmp_a(p,q,r,l) = tmp_a(p,q,r,l) + tmp_b(p,q,k,l)*C(r,k) + end do + end do + end do + end do + end do + + ! (pq|rl) -> (pq|rs) + tmp_b(:,:,:,:) = 0.0_dp + pq = 0 + do p = 1, n + do q = 1, n + pq = eri_ind(p,q) + do r = 1, n + do l = 1, n + do s = 1, n + rs = eri_ind(r,s) + tmp_b(p,q,r,s) = tmp_b(p,q,r,s) + tmp_a(p,q,r,l)*C(s,l) + end do + end do + end do + end do + end do + + pq = 0 + pqrs = 0 + do p = 1, n + do q = 1, p + pq = pq + 1 + do r = 1, p + if (p==r) then + ! If p==r, then s must be smaller than q for rs <= pq + s_up = q + else + ! Default rules + s_up = r + end if + do s = 1, s_up + pqrs = pqrs + 1 + eri_mo(pqrs) = tmp_b(p,q,r,s) + end do + end do + end do + end do + end associate + + nocc = sys%nel/2 + associate(e=>sys%canon_levels, eri=>int_store%eri_mo, emp=>sys%e_mp2) + do i = 1, nocc + do j = 1, nocc + do a = nocc+1, n + ia = eri_ind(i,a) + ja = eri_ind(j,a) + do b = nocc+1, n + jb = eri_ind(j,b) + ib = eri_ind(i,b) + emp = emp+(eri(eri_ind(ia,jb))*(2*eri(eri_ind(ia,jb))-eri(eri_ind(ib,ja))))& + / (e(i)+e(j)-e(a)-e(b)) + end do + end do + end do + end do + end associate + print*, sys%e_mp2 + + end subroutine do_mp2 + + + +end module mp2 \ No newline at end of file diff --git a/src/read_in_integrals.f90 b/src/read_in_integrals.f90 index 710c3de..a7e4ce6 100644 --- a/src/read_in_integrals.f90 +++ b/src/read_in_integrals.f90 @@ -11,6 +11,7 @@ module read_in_integrals real(p), allocatable :: core_hamil(:,:) ! Too big, we compress with symmetry real(p), allocatable :: eri(:) + real(p), allocatable :: eri_mo(:) end type int_store_t contains @@ -23,7 +24,8 @@ subroutine read_integrals_in(sys, int_store) type(system_t), intent(inout) :: sys character(20) :: enuc_f, ovlp_f, ke_f, ele_nuc_f, eri_f - integer :: i, j, iunit, ir, natoms, ios, nbasis, ibasis, jbasis, abasis, bbasis + integer :: i, j, iunit, ir, natoms, ios, nbasis + integer :: ibasis, jbasis, abasis, bbasis, ij_ind, ab_ind real(p) :: intgrl ! stdout unit is 6 @@ -121,7 +123,9 @@ subroutine read_integrals_in(sys, int_store) ! If EOF reached if (ios==iostat_end) exit ! 8-fold permutational symmetry, we use compression to save space - int_store%eri(eri_ind(ibasis, jbasis, abasis, bbasis)) = intgrl + ij_ind = eri_ind(ibasis, jbasis) + ab_ind = eri_ind(abasis, bbasis) + int_store%eri(eri_ind(ij_ind, ab_ind)) = intgrl end do close(ir) @@ -149,29 +153,20 @@ subroutine init_int_store(sys, int_store) end associate end subroutine init_int_store - elemental function eri_ind(i, j, a, b) result(ind) - integer, intent(in) :: i, j, a, b - integer :: ind + elemental function eri_ind(i, j) result(ind) + ! This function can be a general version for i,j,a,b, but + ! we can also use storage to cut down on unnecessary instructrions: + ! i.e. by storing intermediate results ij and ab - integer :: ij, ab + integer, intent(in) :: i, j + integer :: ind if (i >= j) then - ij = i*(i-1)/2 + j + ind = i*(i-1)/2 + j else - ij = j*(j-1)/2 + i + ind = j*(j-1)/2 + i end if - if (a >= b) then - ab = a*(a-1)/2 + b - else - ab = b*(b-1)/2 + a - end if - - if (ij >= ab) then - ind = ij*(ij-1)/2 + ab - else - ind = ab*(ab-1)/2 + ij - end if end function eri_ind subroutine print_sys_info(sys, int_store) diff --git a/src/system.f90 b/src/system.f90 index b8dde9b..c3c72d5 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -4,12 +4,25 @@ module system implicit none type system_t + ! Basic system information integer :: nel = 0 integer :: nbasis = 0 integer :: natoms = 0 - integer, allocatable :: charges(:) real(p), allocatable :: coords(:,:) + + ! Calculation info + real(p) :: e_hf = 0.0_p + real(p) :: e_mp2 = 0.0_p + real(p) :: e_ccsd = 0.0_p + real(p) :: e_ccsd_t = 0.0_p + + ! Coefficient matrix of the canonical HF orbitals in the original, nonorthogonal AO basis + real(p), allocatable :: canon_coeff(:,:) + real(p), allocatable :: canon_levels(:) + + + end type system_t type state_t From 1d753e341a90894d955967175fe4f4a0e53fd2e1 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 19 Dec 2021 11:39:40 +0000 Subject: [PATCH 13/71] More printing, eri lookup array --- src/main.F90 | 19 +++++++++++++++++-- src/mp2.f90 | 13 ++++++++++--- src/read_in_integrals.f90 | 21 +++++++++++++++++++-- 3 files changed, 46 insertions(+), 7 deletions(-) diff --git a/src/main.F90 b/src/main.F90 index fe79bbb..e4dd264 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -33,18 +33,33 @@ program main call print_sys_info(sys, int_store) call system_clock(t1) if (t1sys%canon_levels, eri=>int_store%eri_mo, emp=>sys%e_mp2) do i = 1, nocc @@ -205,7 +212,7 @@ subroutine do_mp2(sys, int_store) end do end do end associate - print*, sys%e_mp2 + write(iunit, '(1X, A, 1X, F15.8)') 'MP2 correlation energy (Hartree):', sys%e_mp2 end subroutine do_mp2 diff --git a/src/read_in_integrals.f90 b/src/read_in_integrals.f90 index a7e4ce6..0a61df4 100644 --- a/src/read_in_integrals.f90 +++ b/src/read_in_integrals.f90 @@ -3,6 +3,12 @@ module read_in_integrals implicit none + public + private :: ioff + + integer, parameter :: bignum = 1000 + integer :: ioff(bignum) + type int_store_t real(p) :: e_nuc = 0.0_p real(p), allocatable :: ovlp(:,:) @@ -118,6 +124,8 @@ subroutine read_integrals_in(sys, int_store) write(iunit, *) 'Reading two-body integrals...' open(newunit=ir, file=eri_f, status='old', form='formatted') + call init_ioff() + do read(ir, *, iostat=ios) ibasis, jbasis, abasis, bbasis, intgrl ! If EOF reached @@ -153,6 +161,15 @@ subroutine init_int_store(sys, int_store) end associate end subroutine init_int_store + subroutine init_ioff() + integer :: i + + ioff(1) = 1 + do i = 2, bignum + ioff(i) = ioff(i-1) + i-1 + end do + end subroutine + elemental function eri_ind(i, j) result(ind) ! This function can be a general version for i,j,a,b, but ! we can also use storage to cut down on unnecessary instructrions: @@ -162,9 +179,9 @@ elemental function eri_ind(i, j) result(ind) integer :: ind if (i >= j) then - ind = i*(i-1)/2 + j + ind = ioff(i) + j-1 else - ind = j*(j-1)/2 + i + ind = ioff(j) + i-1 end if end function eri_ind From 1cce7cd25343ff7acc98c831750b97dad916ea9b Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 19 Dec 2021 21:26:07 +0000 Subject: [PATCH 14/71] Fix geometry, update readme --- README.md | 15 +++++++++++++++ src/geometry.f90 | 12 +++++++----- src/main.F90 | 12 ++++++------ src/read_in_integrals.f90 | 2 +- 4 files changed, 29 insertions(+), 12 deletions(-) diff --git a/README.md b/README.md index 138c9bd..dd6855a 100644 --- a/README.md +++ b/README.md @@ -1,3 +1,18 @@ # A Fortran Electronic Structure Programme (AFESP) This project is based on the Crawford Group's excellent [C++ Programming Tutorial in Chemistry](https://github.com/CrawfordGroup/ProgrammingProjects), but written in Fortran. The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as per the original tutorial, but with additional support for multicore processors (modern CPUs, GPUs). + +## Progress +~~1. Geometry read-in~~ +~~2. Integral read-in~~ +~~3. Nuclear repulsion energy calculation~~ +~~4. Hartree-Fock without symmetry~~ +~~5. Pretty printing, time reporting~~ +~~6. MP2 without symmetry~~ +7. CCSD without symmetry +8. Adapting Hartree-Fock with symmetry +9. Ditto for MP2 +10. Ditto for CCSD +11. CCSD(T) with symmetry +12. OpenMP / MPI parallelisation +13. GPU adaptation for MP2 and CCSD/(T) diff --git a/src/geometry.f90 b/src/geometry.f90 index 417fd83..4eaf62a 100644 --- a/src/geometry.f90 +++ b/src/geometry.f90 @@ -42,14 +42,16 @@ subroutine read_geometry_in(sys, int_store) end subroutine read_geometry_in - subroutine get_bond_lengths(coords, bondlengths) - real(p), intent(in) :: coords(:,:) + subroutine get_bond_lengths(sys, bondlengths) + use system, only: system_t + + type(system_t), intent(in) :: sys real(p), allocatable, intent(out) :: bondlengths(:,:) integer :: i, j ! Negligible memeory cost to store the full matrix rather than the lower triangular - associate(natoms=>size(coords, dim=1)) + associate(natoms=>sys%natoms, coords=>sys%coords) allocate(bondlengths(natoms, natoms), source=0.0_p) do i = 1, natoms-1 @@ -71,10 +73,10 @@ subroutine get_e_nuc(sys, e_nuc) integer :: i, j - call get_bond_lengths(sys%coords, bondlengths) + call get_bond_lengths(sys, bondlengths) e_nuc = 0.0_p - do j = 2, size(sys%charges) + do j = 2, sys%natoms do i = 1, j-1 e_nuc = e_nuc + sys%charges(i)*sys%charges(j)/bondlengths(i,j) end do diff --git a/src/main.F90 b/src/main.F90 index e4dd264..d0f5d7d 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -50,13 +50,13 @@ program main write(iunit, '(1X, 64("="))') write(iunit, '(1X, A)') 'Final energy breakdown' - write(iunit, '(1X, A24, 1X, F15.7)') 'E_HF:', sys%e_hf - write(iunit, '(1X, A24, 1X, F15.7)') 'E_MP2:', sys%e_mp2 - write(iunit, '(1X, A24, 1X, F15.7)') 'E_CCSD:', sys%e_ccsd - write(iunit, '(1X, A24, 1X, F15.7)') 'E_CCSD(T):', sys%e_ccsd_t + write(iunit, '(1X, A, 1X, F12.7)') 'E_HF: ', sys%e_hf + write(iunit, '(1X, A, 1X, F12.7)') 'E_MP2: ', sys%e_mp2 + write(iunit, '(1X, A, 1X, F12.7)') 'E_CCSD: ', sys%e_ccsd + write(iunit, '(1X, A, 1X, F12.7)') 'E_CCSD(T): ', sys%e_ccsd_t write(iunit, '(1X, 40("-"))') - write(iunit, '(1X, A24, 1X, F15.7)') 'Total electronic energy:', sys%e_hf+sys%e_mp2+sys%e_ccsd+sys%e_ccsd_t - write(iunit, '(1X, A24, 1X, F15.7)') 'Total energy:', sys%e_hf+sys%e_mp2+sys%e_ccsd+sys%e_ccsd_t + int_store%e_nuc + write(iunit, '(1X, A, 1X, F12.7)') 'Total electronic energy:', sys%e_hf+sys%e_mp2+sys%e_ccsd+sys%e_ccsd_t + write(iunit, '(1X, A, 1X, F12.7)') 'Total energy: ', sys%e_hf+sys%e_mp2+sys%e_ccsd+sys%e_ccsd_t + int_store%e_nuc call date_and_time(VALUES=date_values) write(iunit, '(1X, 64("="))') diff --git a/src/read_in_integrals.f90 b/src/read_in_integrals.f90 index 0a61df4..0628798 100644 --- a/src/read_in_integrals.f90 +++ b/src/read_in_integrals.f90 @@ -4,7 +4,7 @@ module read_in_integrals implicit none public - private :: ioff + private :: ioff, bignum integer, parameter :: bignum = 1000 integer :: ioff(bignum) From e41274ae3c120ab5924651df34fa7e2b770a57bf Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 19 Dec 2021 21:28:51 +0000 Subject: [PATCH 15/71] Update README.md --- README.md | 26 +++++++++++++------------- 1 file changed, 13 insertions(+), 13 deletions(-) diff --git a/README.md b/README.md index dd6855a..f6c56c5 100644 --- a/README.md +++ b/README.md @@ -3,16 +3,16 @@ This project is based on the Crawford Group's excellent [C++ Programming Tutoria The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as per the original tutorial, but with additional support for multicore processors (modern CPUs, GPUs). ## Progress -~~1. Geometry read-in~~ -~~2. Integral read-in~~ -~~3. Nuclear repulsion energy calculation~~ -~~4. Hartree-Fock without symmetry~~ -~~5. Pretty printing, time reporting~~ -~~6. MP2 without symmetry~~ -7. CCSD without symmetry -8. Adapting Hartree-Fock with symmetry -9. Ditto for MP2 -10. Ditto for CCSD -11. CCSD(T) with symmetry -12. OpenMP / MPI parallelisation -13. GPU adaptation for MP2 and CCSD/(T) +- [x] Geometry read-in +- [x] Integral read-in +- [x] Nuclear repulsion energy calculation +- [x] Hartree-Fock without symmetry +- [x] Pretty printing, time reporting +- [x] MP2 without symmetry +- [ ] CCSD without symmetry +- [ ] Adapting Hartree-Fock with symmetry +- [ ] Ditto for MP2 +- [ ] Ditto for CCSD +- [ ] CCSD(T) with symmetry +- [ ] OpenMP / MPI parallelisation +- [ ] GPU adaptation for MP2 and CCSD/(T) From 7ec142a46fe20619ff2fcc3e1efe099f1ec4944b Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 20 Dec 2021 18:29:57 +0000 Subject: [PATCH 16/71] Spatial to spinorbital transformation for CCSD --- src/ccsd.f90 | 118 +++++++++++++++++++ src/geometry.f90 | 2 +- src/hf.f90 | 15 ++- src/{read_in_integrals.f90 => integrals.f90} | 5 +- src/linalg.f90 | 9 ++ src/main.F90 | 2 +- src/mp2.f90 | 8 +- 7 files changed, 148 insertions(+), 11 deletions(-) create mode 100644 src/ccsd.f90 rename src/{read_in_integrals.f90 => integrals.f90} (98%) diff --git a/src/ccsd.f90 b/src/ccsd.f90 new file mode 100644 index 0000000..d709fbc --- /dev/null +++ b/src/ccsd.f90 @@ -0,0 +1,118 @@ +module ccsd + + use const + + implicit none + + contains + + subroutine do_ccsd(sys, int_store) + use system, only: system_t + use integrals, only: int_store_t, eri_ind + + type(system_t), intent(in) :: sys + type(int_store_t), intent(inout) :: int_store + integer :: p, q, r, s + integer :: pr, qr, pa, pb, qa, qb, ra, rb, sa, sb + real(dp) :: a, b + integer, parameter :: iunit = 6 + + write(iunit, '(1X, 10("-"))') + write(iunit, '(1X, A)') 'CCSD' + write(iunit, '(1X, 10("-"))') + + write(iunit, '(1X, A)') 'Performing spatial to spinorbital MO ERI transformation...' + + !if (.false.) then + ! Permutational symmetry hurts my brain, let's get a naive version working first + !associate(n=>sys%nbasis, asym=>int_store%asym_spinorb, eri=>int_store%eri_mo) + ! [TODO]: this isn't necessary but easier for debugging, change to spin lookup arrays or something similar + !allocate(asym(n*2,n*2,n*2,n*2), source=0.0_dp) + !do p = 1, n + ! pa = 2*p-1 + ! do q = 1, p + ! qa = 2*q-1 + ! do r = 1, p + ! ra = 2*r-1 + ! pr = eri_ind(p,r) + ! qr = eri_ind(q,r) + ! if (r==p) then + ! s_up = q + ! else + ! s_up = r + ! end if + ! do s = 1, s_up + ! sa = 2*s-1 + ! prqs = eri(eri_ind(pr, eri_ind(q,s))) + ! psqr = eri(eri_ind(eri_ind(p,s), qr)) + ! + ! ! nonzero: = - = = - + ! asym(pa,qa,ra,sa) = prqs - psqr + ! asym(pa,qa,sa,ra) = psqr - prqs + ! asym(ra,sa,pa,qa) = prqs - psqr + ! asym(sa,ra,pa,qa) = psqr - prqs + + ! nonzero + ! asym(pa+1,qa+1,ra+1,sa+1) = prqs - psqr + ! asym(pa+1,qa+1,sa+1,ra+1) = psqr - prqs + ! asym(ra+1,sa+1,pa+1,qa+1) = prqs - psqr + ! asym(sa+1,ra+1,pa+1,qa+1) = psqr - prqs + + ! nonzero: = , = - etc + ! asym(pa,qa+1,ra,sa+1) = prqs + ! asym(pa,qa+1,sa+1,ra) = -prqs + ! asym(ra,sa+1,pa,qa+1) = prqs + ! asym(sa+1,ra,pa,qa+1) = -prqs + + ! nonzero + ! asym(pa+1,qa,ra+1,sa) = prqs + ! asym(pa+1,qa,sa,ra+1) = -prqs + ! asym(ra+1,sa,pa+1,qa) = prqs + ! asym(sa,ra+1,pa+1,qa) = -prqs + ! end do + ! end do + ! end do + !end do + !end associate + !end if + + associate(n=>sys%nbasis, asym=>int_store%asym_spinorb, eri=>int_store%eri_mo) + ! [TODO]: this isn't necessary but easier for debugging, change to spin lookup arrays or something similar + allocate(int_store%asym_spinorb(n*2,n*2,n*2,n*2), source=0.0_dp) + do p = 1, n + pa = 2*p-1 + pb = pa+1 + + do q = 1, n + qa = 2*q-1 + qb = qa+1 + + do r = 1, n + ra = 2*r-1 + rb = ra+1 + + pr = eri_ind(p,r) + qr = eri_ind(q,r) + + do s = 1, n + sa = 2*s-1 + sb = sa+1 + a = eri(eri_ind(pr,eri_ind(q,s))) + b = eri(eri_ind(eri_ind(p,s),qr)) + ! Draw a spin decision tree to visualise + asym(pa,qa,ra,sa) = a-b + asym(pb,qb,rb,sb) = a-b + asym(pa,qb,ra,sb) = a + asym(pb,qa,rb,sa) = a + asym(pa,qb,rb,sa) = -b + asym(pb,qa,ra,sb) = -b + end do + end do + end do + end do + end associate + + end subroutine do_ccsd + + +end module ccsd \ No newline at end of file diff --git a/src/geometry.f90 b/src/geometry.f90 index 4eaf62a..c5fc594 100644 --- a/src/geometry.f90 +++ b/src/geometry.f90 @@ -8,7 +8,7 @@ module geometry subroutine read_geometry_in(sys, int_store) ! Read in geometry data supplied in a file use system, only: system_t - use read_in_integrals, only: int_store_t + use integrals, only: int_store_t type(system_t), intent(inout) :: sys type(int_store_t), intent(inout) :: int_store diff --git a/src/hf.f90 b/src/hf.f90 index e2217fe..4913455 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -7,7 +7,7 @@ module hf subroutine do_hartree_fock(sys, int_store) use error_handling use system - use read_in_integrals + use integrals use linalg type(int_store_t), intent(in) :: int_store @@ -40,7 +40,9 @@ subroutine do_hartree_fock(sys, int_store) ! S^(-1/2) = C * L^(-1/2) * C^(T) call diagonalise(ovlp) + !call zero_mat(ovlp%A) call build_ortmat(ovlp, ortmat) + !call zero_mat(ortmat) call deallocate_mat_t(ovlp) @@ -50,14 +52,17 @@ subroutine do_hartree_fock(sys, int_store) do iter = 1, maxiter fockmat%ao_ort = matmul(transpose(ortmat), matmul(fockmat%ao, ortmat)) + !call zero_mat(fockmat%ao_ort) call diagonalise(fockmat) ! Transform coefficient into nonorthogonal AO basis fockmat%A = transpose(matmul(ortmat, fockmat%A)) + !call zero_mat(fockmat%A) ! [TODO]: this is just hard-coded for now for water, URGENT: add geom_read_in call build_density(fockmat%A, density, 5) + !call zero_mat(density) call update_scf_energy(density, fockmat%ao, st, int_store, conv) if (conv) then @@ -78,6 +83,7 @@ subroutine do_hartree_fock(sys, int_store) end if call build_fock(sys, density, fockmat%ao, int_store) + !call zero_mat(fockmat%ao) end do if (.not. conv) then @@ -102,11 +108,12 @@ subroutine diagonalise(mat) mat%A = mat%ao_ort call eigs(mat, ierr) if (ierr /= 0) call error('hf::diagonalise', 'Diagonalisation failed!') + !call zero_mat(mat%A) end subroutine diagonalise subroutine init_mat_t(matrix, mat) - use read_in_integrals + use integrals use linalg, only: mat_t use system @@ -173,7 +180,7 @@ end subroutine build_density subroutine update_scf_energy(density, fock, st, int_store, conv) use system, only: state_t - use read_in_integrals, only: int_store_t + use integrals, only: int_store_t real(p), intent(in) :: density(:,:) real(p), intent(in) :: fock(:,:) @@ -193,7 +200,7 @@ end subroutine update_scf_energy subroutine build_fock(sys, density, fock, int_store) - use read_in_integrals, only: int_store_t, eri_ind + use integrals, only: int_store_t, eri_ind use system, only: system_t real(p), intent(in) :: density(:,:) diff --git a/src/read_in_integrals.f90 b/src/integrals.f90 similarity index 98% rename from src/read_in_integrals.f90 rename to src/integrals.f90 index 0628798..2df7659 100644 --- a/src/read_in_integrals.f90 +++ b/src/integrals.f90 @@ -1,4 +1,4 @@ -module read_in_integrals +module integrals use const implicit none @@ -18,6 +18,7 @@ module read_in_integrals ! Too big, we compress with symmetry real(p), allocatable :: eri(:) real(p), allocatable :: eri_mo(:) + real(p), allocatable :: asym_spinorb(:,:,:,:) end type int_store_t contains @@ -204,4 +205,4 @@ subroutine print_sys_info(sys, int_store) end subroutine print_sys_info -end module read_in_integrals +end module integrals diff --git a/src/linalg.f90 b/src/linalg.f90 index aea55bc..bc16e60 100644 --- a/src/linalg.f90 +++ b/src/linalg.f90 @@ -34,4 +34,13 @@ subroutine eigs(mat, ierr) deallocate(work) end do end subroutine eigs + + elemental subroutine zero_mat(matel) + ! Zero out entries smaller than machine precision + + real(p), intent(inout) :: matel + + if (abs(matel)sys%canon_levels, eri=>int_store%eri_mo, emp=>sys%e_mp2) From 97cc57f22e01af19f73c448bb593e27bad7f0744 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 20 Dec 2021 21:39:20 +0000 Subject: [PATCH 17/71] Working CCSD initialisation, reproduces MP2 energy --- src/ccsd.f90 | 36 +++++++++++++++++++++++++++++++++--- src/geometry.f90 | 1 + src/hf.f90 | 3 +-- src/main.F90 | 7 +++++++ src/system.f90 | 1 + 5 files changed, 43 insertions(+), 5 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index d709fbc..2a837b5 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -4,6 +4,12 @@ module ccsd implicit none + type cc_amp_t + real(p), allocatable :: diag(:) + real(p), allocatable :: t_ia(:,:) + real(p), allocatable :: t_ijab(:,:,:,:) + end type cc_amp_t + contains subroutine do_ccsd(sys, int_store) @@ -12,9 +18,10 @@ subroutine do_ccsd(sys, int_store) type(system_t), intent(in) :: sys type(int_store_t), intent(inout) :: int_store - integer :: p, q, r, s + integer :: i, p, q, r, s integer :: pr, qr, pa, pb, qa, qb, ra, rb, sa, sb - real(dp) :: a, b + real(dp) :: a, b, e_mp2 + type(cc_amp_t) :: cc_amp integer, parameter :: iunit = 6 write(iunit, '(1X, 10("-"))') @@ -76,9 +83,9 @@ subroutine do_ccsd(sys, int_store) !end associate !end if + allocate(int_store%asym_spinorb(sys%nbasis*2,sys%nbasis*2,sys%nbasis*2,sys%nbasis*2), source=0.0_dp) associate(n=>sys%nbasis, asym=>int_store%asym_spinorb, eri=>int_store%eri_mo) ! [TODO]: this isn't necessary but easier for debugging, change to spin lookup arrays or something similar - allocate(int_store%asym_spinorb(n*2,n*2,n*2,n*2), source=0.0_dp) do p = 1, n pa = 2*p-1 pb = pa+1 @@ -112,6 +119,29 @@ subroutine do_ccsd(sys, int_store) end do end associate + allocate(cc_amp%diag(2*sys%nbasis)) + do i = 1, sys%nbasis + cc_amp%diag(2*i-1:2*i) = sys%canon_levels(i) + end do + + allocate(cc_amp%t_ijab(2*sys%nbasis,2*sys%nbasis,2*sys%nbasis,2*sys%nbasis), source=0.0_dp) + associate(doubles=>cc_amp%t_ijab, nocc=>sys%nocc, n=>sys%nbasis, asym=>int_store%asym_spinorb, e=>cc_amp%diag) + e_mp2 = 0.0_dp + do p = 1, 2*nocc + do q = 1, 2*nocc + do r = 2*nocc+1, 2*n + do s = 2*nocc+1, 2*n + doubles(p,q,r,s) = asym(p,q,r,s)/(e(p)+e(q)-e(r)-e(s)) + e_mp2 = e_mp2 + doubles(p,q,r,s)*asym(p,q,r,s) + end do + end do + end do + end do + print*, e_mp2/4 + end associate + + + end subroutine do_ccsd diff --git a/src/geometry.f90 b/src/geometry.f90 index c5fc594..1e0e895 100644 --- a/src/geometry.f90 +++ b/src/geometry.f90 @@ -36,6 +36,7 @@ subroutine read_geometry_in(sys, int_store) close(ir) sys%nel = sum(sys%charges) + sys%nocc = sys%nel/2 call get_e_nuc(sys, int_store%e_nuc) diff --git a/src/hf.f90 b/src/hf.f90 index 4913455..397f086 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -60,8 +60,7 @@ subroutine do_hartree_fock(sys, int_store) fockmat%A = transpose(matmul(ortmat, fockmat%A)) !call zero_mat(fockmat%A) - ! [TODO]: this is just hard-coded for now for water, URGENT: add geom_read_in - call build_density(fockmat%A, density, 5) + call build_density(fockmat%A, density, sys%nel/2) !call zero_mat(density) call update_scf_energy(density, fockmat%ao, st, int_store, conv) diff --git a/src/main.F90 b/src/main.F90 index d0d3b8f..c3a8a28 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -6,6 +6,7 @@ program main use hf, only: do_hartree_fock use geometry, only: read_geometry_in use mp2, only: do_mp2 + use ccsd, only: do_ccsd implicit none @@ -48,6 +49,12 @@ program main write(iunit, '(1X, A, 1X, F7.5, A)') 'Time taken for MP2:', real(t1-t0)/count_rate, "s" t0=t1 + call do_ccsd(sys, int_store) + call system_clock(t1) + if (t1 = - + ! where = (pr|qs) * delta(sigma_p,sigma_r) * delta(sigma_q,sigma_s) + write(iunit, '(1X, A)') 'Forming antisymmetrised spinorbital ERIs...' + allocate(int_store%asym_spinorb(sys%nbasis*2,sys%nbasis*2,sys%nbasis*2,sys%nbasis*2), source=0.0_dp, stat=ierr) + call check_allocate('int_store%asym_spinorb', sys%nbasis**4*16, ierr) - !if (.false.) then - ! Permutational symmetry hurts my brain, let's get a naive version working first - !associate(n=>sys%nbasis, asym=>int_store%asym_spinorb, eri=>int_store%eri_mo) - ! [TODO]: this isn't necessary but easier for debugging, change to spin lookup arrays or something similar - !allocate(asym(n*2,n*2,n*2,n*2), source=0.0_dp) - !do p = 1, n - ! pa = 2*p-1 - ! do q = 1, p - ! qa = 2*q-1 - ! do r = 1, p - ! ra = 2*r-1 - ! pr = eri_ind(p,r) - ! qr = eri_ind(q,r) - ! if (r==p) then - ! s_up = q - ! else - ! s_up = r - ! end if - ! do s = 1, s_up - ! sa = 2*s-1 - ! prqs = eri(eri_ind(pr, eri_ind(q,s))) - ! psqr = eri(eri_ind(eri_ind(p,s), qr)) - ! - ! ! nonzero: = - = = - - ! asym(pa,qa,ra,sa) = prqs - psqr - ! asym(pa,qa,sa,ra) = psqr - prqs - ! asym(ra,sa,pa,qa) = prqs - psqr - ! asym(sa,ra,pa,qa) = psqr - prqs - - ! nonzero - ! asym(pa+1,qa+1,ra+1,sa+1) = prqs - psqr - ! asym(pa+1,qa+1,sa+1,ra+1) = psqr - prqs - ! asym(ra+1,sa+1,pa+1,qa+1) = prqs - psqr - ! asym(sa+1,ra+1,pa+1,qa+1) = psqr - prqs - - ! nonzero: = , = - etc - ! asym(pa,qa+1,ra,sa+1) = prqs - ! asym(pa,qa+1,sa+1,ra) = -prqs - ! asym(ra,sa+1,pa,qa+1) = prqs - ! asym(sa+1,ra,pa,qa+1) = -prqs - - ! nonzero - ! asym(pa+1,qa,ra+1,sa) = prqs - ! asym(pa+1,qa,sa,ra+1) = -prqs - ! asym(ra+1,sa,pa+1,qa) = prqs - ! asym(sa,ra+1,pa+1,qa) = -prqs - ! end do - ! end do - ! end do - !end do - !end associate - !end if - - allocate(int_store%asym_spinorb(sys%nbasis*2,sys%nbasis*2,sys%nbasis*2,sys%nbasis*2), source=0.0_dp) associate(n=>sys%nbasis, asym=>int_store%asym_spinorb, eri=>int_store%eri_mo) ! [TODO]: this isn't necessary but easier for debugging, change to spin lookup arrays or something similar do p = 1, n @@ -104,34 +68,52 @@ subroutine do_ccsd(sys, int_store) do s = 1, n sa = 2*s-1 sb = sa+1 - a = eri(eri_ind(pr,eri_ind(q,s))) - b = eri(eri_ind(eri_ind(p,s),qr)) + prqs = eri(eri_ind(pr,eri_ind(q,s))) + psqr = eri(eri_ind(eri_ind(p,s),qr)) ! Draw a spin decision tree to visualise - asym(pa,qa,ra,sa) = a-b - asym(pb,qb,rb,sb) = a-b - asym(pa,qb,ra,sb) = a - asym(pb,qa,rb,sa) = a - asym(pa,qb,rb,sa) = -b - asym(pb,qa,ra,sb) = -b + asym(pa,qa,ra,sa) = prqs-psqr + asym(pb,qb,rb,sb) = prqs-psqr + asym(pa,qb,ra,sb) = prqs + asym(pb,qa,rb,sa) = prqs + asym(pa,qb,rb,sa) = -psqr + asym(pb,qa,ra,sb) = -psqr end do end do end do end do end associate - allocate(cc_amp%diag(2*sys%nbasis)) - do i = 1, sys%nbasis - cc_amp%diag(2*i-1:2*i) = sys%canon_levels(i) + ! Forming the energy denominator matrices + associate(n=>sys%nbasis, nocc=>sys%nocc, e=>sys%canon_levels) + allocate(D_ia(2*nocc, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('D_ia', 4*nocc*(n-nocc), ierr) + allocate(D_ijab(2*nocc, 2*nocc, 2*nocc+1:2*n, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('D_ijab', 16*(nocc**2*(n-nocc)**2), ierr) + do i = 1, nocc + do a = nocc+1, n + D_ia(2*i-1:2*i,2*a-1:2*a) = e(i)-e(a) + do j = 1, nocc + do b = nocc+1, n + D_ijab(2*i-1:2*i, 2*j-1:2*j, 2*a-1:2*a, 2*b-1:2*b) = e(i)+e(j)-e(a)-e(b) + end do + end do + end do end do - allocate(cc_amp%t_ijab(2*sys%nbasis,2*sys%nbasis,2*sys%nbasis,2*sys%nbasis), source=0.0_dp) - associate(doubles=>cc_amp%t_ijab, nocc=>sys%nocc, n=>sys%nbasis, asym=>int_store%asym_spinorb, e=>cc_amp%diag) + ! Initialise t_i^a=0 and t_{ij}^{ab}=MP1 WF + allocate(cc_amp%t_ijab(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('cc_amp%t_ijab', 16*(nocc**2*(n-nocc)**2), ierr) + allocate(cc_amp%t_ia(2*nocc, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('cc_amp%t_ia', 4*nocc*(n-nocc), ierr) + end associate + + associate(doubles=>cc_amp%t_ijab, nocc=>sys%nocc, nvirt=>sys%nvirt, asym=>int_store%asym_spinorb) e_mp2 = 0.0_dp do p = 1, 2*nocc do q = 1, 2*nocc - do r = 2*nocc+1, 2*n - do s = 2*nocc+1, 2*n - doubles(p,q,r,s) = asym(p,q,r,s)/(e(p)+e(q)-e(r)-e(s)) + do r = 2*sys%nocc+1, 2*sys%nbasis + do s = 2*sys%nocc+1, 2*sys%nbasis + doubles(p,q,r,s) = asym(p,q,r,s)/D_ijab(p,q,r,s) e_mp2 = e_mp2 + doubles(p,q,r,s)*asym(p,q,r,s) end do end do @@ -140,9 +122,94 @@ subroutine do_ccsd(sys, int_store) print*, e_mp2/4 end associate - + ! Allocate the intermediate quantities + associate(n=>sys%nbasis, nocc=>sys%nocc) + allocate(F_vv(2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('F_vv', 4*(n-nocc)**2, ierr) + allocate(F_oo(2*nocc,2*nocc), source=0.0_dp, stat=ierr) + call check_allocate('F_oo', 4*nocc**2, ierr) + allocate(F_ov(2*nocc,2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('F_ov', 4*nocc*(n-nocc), ierr) + end associate end subroutine do_ccsd + subroutine build_tau(sys, cc_amp, tau, tau_tilde) + type(system_t), intent(in) :: sys + type(cc_amp_t), intent(in) :: cc_amp + real(p), intent(out) :: tau(:,:,:,:), tau_tilde(:,:,:,:) + + integer :: i, j, a, b + real(p) :: ia, ja, x + + associate(n=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) + do i = 1, 2*nocc + do a = 2*nocc+1, 2*n + ia = t_ia(i,a) + do j = 1, 2*nocc + ja = t_ia(j,a) + do b = 2*nocc+1, 2*n + x = ia*t_ia(j,b) - t_ia(i,b)*ja + tau_tilde(i,j,a,b) = t_ijab(i,j,a,b) + 0.5*x + tau(i,j,a,b) = tau_tilde(i,j,a,b) + 0.5*x + end do + end do + end do + end do + end associate + + end subroutine build_tau + + subroutine build_F(sys, F_vv, F_oo, F_ov, cc_amp, asym, tau_tilde) + ! Eqs. 3-5, as we use HF reference all terms involving the fock matrix vanishes + type(system_t), intent(in) :: sys + type(cc_amp_t), intent(in) :: cc_amp + real(p), intent(in) :: asym(:,:,:,:) + real(p), intent(in) :: tau_tilde(:,:,:,:) + real(p), intent(out) :: F_vv(:,:), F_oo(:,:), F_ov(:,:) + + integer :: a, e, f, m, n, i + + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) + ! F_ae = \sum_{mf} t_m^f * - 0.5 \sum_{mnf} \tau~_{mn}^{af} + do a = 2*nocc+1, 2*nbasis + do e = 2*nocc+1, 2*nbasis + do m = 1, 2*nocc + do f = 2*nocc+1, 2*nbasis + F_vv(a,e) = F_vv(a,e) + t_ia(m,f) * asym(m,a,f,e) + do n = 1, 2*nocc + F_vv(a,e) = F_vv(a,e) - 0.5*tau_tilde(m,n,a,f)*asym(m,n,e,f) + end do + end do + end do + end do + end do + + ! F_mi = \sum_{en} t_n^e + 0.5 \sum_{nef} \tau~_{in}^{ef} + do m = 1, 2*nocc + do i = 1, 2*nocc + do e = 2*nocc+1, 2*nbasis + do n = 1, 2*nocc + F_oo(m,i) = F_oo(m,i) + t_ia(n,e)*asym(m,n,i,e) + do f = 2*nocc+1, 2*nbasis + F_oo(m,i) = F_oo(m,i) + 0.5*tau_tilde(i,n,e,f)*asym(m,n,e,f) + end do + end do + end do + end do + end do + + ! F_me = \sum_{nf} t_n^f * + do m = 1, 2*nocc + do e = 2*nocc+1, 2*nbasis + do n = 1, 2*nocc + do f = 2*nocc+1, 2*nbasis + F_ov(m,e) = F_ov(m,e) + t_ia(n,f)*asym(m,n,e,f) + end do + end do + end do + end do + end associate + end subroutine build_F end module ccsd \ No newline at end of file diff --git a/src/error_handling.f90 b/src/error_handling.f90 index 4919d4c..31733b8 100644 --- a/src/error_handling.f90 +++ b/src/error_handling.f90 @@ -18,4 +18,22 @@ subroutine error(procedure, error_msg) return end subroutine error + subroutine check_allocate(array_name, array_size, ierr) + ! Wrapper around an ierr check, so error messages are more helpful. + ! In: + ! array_name: the name of the array being allocated + ! array_size: the intended size of the array + ! ierr: error code returned from allocate() + character(*), intent(in) :: array_name + integer, intent(in) :: array_size + integer, intent(in) :: ierr + + if (array_size < 0 .or. ierr /= 0) then + ! If via some previous calculation array_size is negative we intercept it + write(6, '(1X, A, 1X, A, I0)') 'Error in allocating array', trim(array_name), 'with size', array_size + write(6, '(1X, A, 1X, I0)') 'Error code:', ierr + call error('check_allocate', 'Allocation error') + end if + end subroutine check_allocate + end module error_handling diff --git a/src/geometry.f90 b/src/geometry.f90 index 1e0e895..96c5da7 100644 --- a/src/geometry.f90 +++ b/src/geometry.f90 @@ -37,6 +37,7 @@ subroutine read_geometry_in(sys, int_store) sys%nel = sum(sys%charges) sys%nocc = sys%nel/2 + sys%nvirt = sys%nbasis - sys%nocc call get_e_nuc(sys, int_store%e_nuc) diff --git a/src/system.f90 b/src/system.f90 index 746c786..583da2c 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -9,6 +9,7 @@ module system integer :: nbasis = 0 integer :: natoms = 0 integer :: nocc = 0 + integer :: nvirt = 0 integer, allocatable :: charges(:) real(p), allocatable :: coords(:,:) From 73cce38ffc95b884f9388a83b971e48b409219b0 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Thu, 23 Dec 2021 14:40:47 +0000 Subject: [PATCH 19/71] Form intermediate W tensors, non-lazy allocation of large arrays --- src/ccsd.f90 | 56 ++++++++++++++++++++++++++++++++++++++++++++++++++++ 1 file changed, 56 insertions(+) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index c2a396d..6ce5969 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -130,6 +130,10 @@ subroutine do_ccsd(sys, int_store) call check_allocate('F_oo', 4*nocc**2, ierr) allocate(F_ov(2*nocc,2*nocc+1:2*n), source=0.0_dp, stat=ierr) call check_allocate('F_ov', 4*nocc*(n-nocc), ierr) + allocate(W_oooo(2*nocc,2*nocc,2*nocc,2*nocc), source=0.0_dp, stat=ierr) + call check_allocate('W_oooo', 16*nocc**4, ierr) + allocate(W_ovvo(2*nocc,2*nocc+1:2*n,2*nocc+1:2*n,2*nocc), source=0.0_dp, stat=ierr) + call check_allocate('W_ovvo', 16*nocc**2*(n-nocc)**2, ierr) end associate end subroutine do_ccsd @@ -212,4 +216,56 @@ subroutine build_F(sys, F_vv, F_oo, F_ov, cc_amp, asym, tau_tilde) end associate end subroutine build_F + subroutine build_W(sys, W_oooo, W_ovvo, cc_amp, asym, tau) + ! Eqs. 6 and 8 + type(system_t), intent(in) :: sys + type(cc_amp_t), intent(in) :: cc_amp + real(p), intent(in) :: asym(:,:,:,:) + real(p), intent(in) :: tau(:,:,:,:) + real(p), intent(out) :: W_oooo(:,:,:,:), W_ovvo(:,:,:,:) + + integer :: m, n, i, j, e, f, b + real(p) :: x + + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) + do m = 1, 2*nocc + do n = 1, 2*nocc + do i = 1, 2*nocc + do j = 1, 2*nocc + W_oooo(m,n,i,j) = asym(m,n,i,j) + do e = 2*nocc+1, 2*nbasis + W_oooo(m,n,i,j) = W_oooo(m,n,i,j) + t_ia(j,e)*asym(m,n,i,e) - t_ia(i,e)*asym(m,n,j,e) + do f = 2*nocc+1, 2*nbasis + W_oooo(m,n,i,j) = W_oooo(m,n,i,j) + 0.5*t_ijab(i,j,e,f)*asym(m,n,e,f) + end do + end do + end do + end do + end do + end do + + do m = 1, 2*nocc + do b = 2*nocc+1, 2*nbasis + do e = 2*nocc+1, 2*nbasis + do j = 1, 2*nocc + W_ovvo(m,b,e,j) = asym(m,b,e,j) + do f = 2*nocc+1, 2*nbasis + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) + t_ia(j,f)*asym(m,b,e,f) + end do + + do n = 1, 2*nbasis + x = t_ia(n,b) + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - x*asym(m,n,e,j) + do f = 2*nocc+1, 2*nbasis + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t_ijab(j,n,f,b) + x*t_ia(j,f)) * asym(m,n,e,f) + end do + end do + end do + end do + end do + end do + + end associate + end subroutine build_W + end module ccsd \ No newline at end of file From a7cf364911a4c01b19e9fe46ea36bacb1c393ace Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sat, 25 Dec 2021 16:45:49 +0000 Subject: [PATCH 20/71] Bug free CCSD but wrong results for now --- src/ccsd.f90 | 261 +++++++++++++++++++++++++++++++++++++++++---------- 1 file changed, 212 insertions(+), 49 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 6ce5969..6700903 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -9,6 +9,19 @@ module ccsd real(p), allocatable :: t_ia(:,:) real(p), allocatable :: t_ijab(:,:,:,:) end type cc_amp_t + + type cc_int_t + ! Intermediate quantities + ! Curly F tensors (Eqs. 3-5) + real(dp), allocatable :: F_oo(:,:), F_vv(:,:), F_ov(:,:) + ! Curly W tensors (Eqs. 6,8), see Appendix for why 7 is avoided + real(dp), allocatable :: W_oooo(:,:,:,:), W_ovvo(:,:,:,:) + ! Effective two-particle excitation operators tau and tilde tau (Eqs. 9-10) + real(dp), allocatable :: tau_tilde(:,:,:,:), tau(:,:,:,:) + ! Energy denominators (Eqs. 12-13) + real(dp), allocatable :: D_ia(:,:), D_ijab(:,:,:,:) + real(dp), allocatable :: tmp_tia(:,:), tmp_tijab(:,:,:,:) + end type cc_int_t contains @@ -18,25 +31,22 @@ subroutine do_ccsd(sys, int_store) use integrals, only: int_store_t, eri_ind use error_handling, only: check_allocate + use system, only: state_t type(system_t), intent(in) :: sys type(int_store_t), intent(inout) :: int_store - integer :: i, j, a, b, p, q, r, s, rasym, sasym + integer :: i, j, a, b, p, q, r, s integer :: pr, qr, pa, pb, qa, qb, ra, rb, sa, sb - real(dp) :: prqs, psqr, e_mp2 + real(dp) :: prqs, psqr + + type(state_t) :: st + type(cc_amp_t) :: cc_amp - integer :: ierr + integer :: ierr, iter integer, parameter :: iunit = 6 + integer, parameter :: maxiter = 50 - ! Intermediate quantities - ! Curly F tensors (Eqs. 3-5) - real(dp), allocatable :: F_oo(:,:), F_vv(:,:), F_ov(:,:) - ! Curly W tensors (Eqs. 6,8), see Appendix for why 7 is avoided - real(dp), allocatable :: W_oooo(:,:,:,:), W_ovvo(:,:,:,:) - ! Effective two-particle excitation operators tau and tilde tau (Eqs. 9-10) - real(dp), allocatable :: tau_til(:,:,:,:), tau(:,:,:,:) - ! Energy denominators (Eqs. 12-13) - real(dp), allocatable :: D_ia(:,:), D_ijab(:,:,:,:) + type(cc_int_t) :: cc_int write(iunit, '(1X, 10("-"))') write(iunit, '(1X, A)') 'CCSD' @@ -83,18 +93,46 @@ subroutine do_ccsd(sys, int_store) end do end associate + call init_cc(sys, int_store, cc_amp, cc_int) + + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab, asym=>int_store%asym_spinorb) + do iter = 1, maxiter + ! Update intermediate tensors + call build_tau(sys, cc_amp, cc_int) + call build_F(sys, cc_int, cc_amp, asym) + call build_W(sys, cc_int, cc_amp, asym) + + call update_amplitudes(sys, cc_amp, int_store, cc_int) + call update_cc_energy(sys, st, int_store, cc_amp) + print*, st%energy + end do + end associate + + end subroutine do_ccsd + + subroutine init_cc(sys, int_store, cc_amp, cc_int) + use integrals, only: int_store_t + use error_handling, only: check_allocate + + type(system_t), intent(in) :: sys + type(int_store_t), intent(in) :: int_store + type(cc_amp_t), intent(inout) :: cc_amp + type(cc_int_t), intent(inout) :: cc_int + + integer :: p, q, r, s, i, j, a, b, ierr + ! Forming the energy denominator matrices associate(n=>sys%nbasis, nocc=>sys%nocc, e=>sys%canon_levels) - allocate(D_ia(2*nocc, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('D_ia', 4*nocc*(n-nocc), ierr) - allocate(D_ijab(2*nocc, 2*nocc, 2*nocc+1:2*n, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('D_ijab', 16*(nocc**2*(n-nocc)**2), ierr) + allocate(cc_int%D_ia(2*nocc, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%D_ia', 4*nocc*(n-nocc), ierr) + allocate(cc_int%D_ijab(2*nocc, 2*nocc, 2*nocc+1:2*n, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%D_ijab', 16*(nocc**2*(n-nocc)**2), ierr) do i = 1, nocc do a = nocc+1, n - D_ia(2*i-1:2*i,2*a-1:2*a) = e(i)-e(a) + cc_int%D_ia(2*i-1:2*i,2*a-1:2*a) = e(i)-e(a) do j = 1, nocc do b = nocc+1, n - D_ijab(2*i-1:2*i, 2*j-1:2*j, 2*a-1:2*a, 2*b-1:2*b) = e(i)+e(j)-e(a)-e(b) + cc_int%D_ijab(2*i-1:2*i, 2*j-1:2*j, 2*a-1:2*a, 2*b-1:2*b) = e(i)+e(j)-e(a)-e(b) end do end do end do @@ -103,50 +141,177 @@ subroutine do_ccsd(sys, int_store) ! Initialise t_i^a=0 and t_{ij}^{ab}=MP1 WF allocate(cc_amp%t_ijab(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) call check_allocate('cc_amp%t_ijab', 16*(nocc**2*(n-nocc)**2), ierr) + allocate(cc_int%tmp_tijab, mold=cc_amp%t_ijab, stat=ierr) + call check_allocate('cc_int%tmp_tijab', 16*(nocc**2*(n-nocc)**2), ierr) allocate(cc_amp%t_ia(2*nocc, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) call check_allocate('cc_amp%t_ia', 4*nocc*(n-nocc), ierr) + allocate(cc_int%tmp_tia, mold=cc_amp%t_ia, stat=ierr) + call check_allocate('cc_int%tmp_tia', 4*nocc*(n-nocc), ierr) end associate - associate(doubles=>cc_amp%t_ijab, nocc=>sys%nocc, nvirt=>sys%nvirt, asym=>int_store%asym_spinorb) - e_mp2 = 0.0_dp + associate(doubles=>cc_amp%t_ijab, nocc=>sys%nocc, asym=>int_store%asym_spinorb) do p = 1, 2*nocc do q = 1, 2*nocc do r = 2*sys%nocc+1, 2*sys%nbasis do s = 2*sys%nocc+1, 2*sys%nbasis - doubles(p,q,r,s) = asym(p,q,r,s)/D_ijab(p,q,r,s) - e_mp2 = e_mp2 + doubles(p,q,r,s)*asym(p,q,r,s) + doubles(p,q,r,s) = asym(p,q,r,s)/cc_int%D_ijab(p,q,r,s) end do end do end do end do - print*, e_mp2/4 end associate - ! Allocate the intermediate quantities + ! Allocate the intermediate tensors associate(n=>sys%nbasis, nocc=>sys%nocc) - allocate(F_vv(2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('F_vv', 4*(n-nocc)**2, ierr) - allocate(F_oo(2*nocc,2*nocc), source=0.0_dp, stat=ierr) - call check_allocate('F_oo', 4*nocc**2, ierr) - allocate(F_ov(2*nocc,2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('F_ov', 4*nocc*(n-nocc), ierr) - allocate(W_oooo(2*nocc,2*nocc,2*nocc,2*nocc), source=0.0_dp, stat=ierr) - call check_allocate('W_oooo', 16*nocc**4, ierr) - allocate(W_ovvo(2*nocc,2*nocc+1:2*n,2*nocc+1:2*n,2*nocc), source=0.0_dp, stat=ierr) - call check_allocate('W_ovvo', 16*nocc**2*(n-nocc)**2, ierr) + allocate(cc_int%F_vv(2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%F_vv', 4*(n-nocc)**2, ierr) + allocate(cc_int%F_oo(2*nocc,2*nocc), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%F_oo', 4*nocc**2, ierr) + allocate(cc_int%F_ov(2*nocc,2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%F_ov', 4*nocc*(n-nocc), ierr) + allocate(cc_int%W_oooo(2*nocc,2*nocc,2*nocc,2*nocc), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%W_oooo', 16*nocc**4, ierr) + allocate(cc_int%W_ovvo(2*nocc,2*nocc+1:2*n,2*nocc+1:2*n,2*nocc), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%W_ovvo', 16*nocc**2*(n-nocc)**2, ierr) + allocate(cc_int%tau(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%tau', 16*nocc**2*(n-nocc)**2, ierr) + allocate(cc_int%tau_tilde(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%tau_tilde', 16*nocc**2*(n-nocc)**2, ierr) end associate - end subroutine do_ccsd + end subroutine init_cc + + subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) + use integrals, only: int_store_t - subroutine build_tau(sys, cc_amp, tau, tau_tilde) type(system_t), intent(in) :: sys + type(int_store_t), intent(in) :: int_store + type(cc_amp_t), intent(inout) :: cc_amp + type(cc_int_t), intent(inout) :: cc_int + + integer :: i, j, a, b, m, n, e, f + real(p) :: W_abef + + associate(tmp_t1=>cc_int%tmp_tia,tmp_t2=>cc_int%tmp_tijab,t1=>cc_amp%t_ia,t2=>cc_amp%t_ijab,asym=>int_store%asym_spinorb, & + F_oo=>cc_int%F_oo,F_ov=>cc_int%F_ov,F_vv=>cc_int%F_vv,D_ia=>cc_int%D_ia,D_ijab=>cc_int%D_ijab,W_oooo=>cc_int%W_oooo, & + W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nbasis=>sys%nbasis) + + ! Update T1 + tmp_t1 = 0.0_dp + do i = 1, 2*nocc + do a = 2*nocc+1, 2*nbasis + do m = 1, 2*nocc + tmp_t1(i,a) = tmp_t1(i,a) - t1(m,a)*F_oo(m,i) + do e = 2*nocc+1, 2*nbasis + tmp_t1(i,a) = tmp_t1(i,a) + t2(i,m,a,e)*F_ov(m,e) + do f = 2*nocc+1, 2*nbasis + tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(i,m,e,f)*asym(m,a,e,f) + end do + do n = 1, 2*nocc + tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(m,n,a,e)*asym(n,m,e,i) + end do + end do + end do + do e = 2*nocc+1, 2*nbasis + tmp_t1(i,a) = tmp_t1(i,a) + t1(i,e)*F_vv(a,e) + do n = 1, 2*nocc + tmp_t1(i,a) = tmp_t1(i,a) - t1(n,e)*asym(n,a,i,e) + end do + end do + end do + end do + t1 = tmp_t1/D_ia + + ! Update T2 + tmp_t2 = 0.0_dp + do i = 1, 2*nocc + do j = 1, 2*nocc + do a = 2*nocc+1, 2*nbasis + do b = 2*nocc+1, 2*nbasis + tmp_t2(i,j,a,b) = asym(i,j,a,b) + do e = 2*nocc+1, 2*nbasis + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + t2(i,j,a,e)*F_vv(b,e) - t2(i,j,b,e)*F_vv(a,e) & + + t1(i,e)*asym(a,b,e,j) - t1(j,e)*asym(a,b,e,i) + do m = 1, 2*nocc + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,j,a,e)*t1(m,b)-& + t2(i,j,b,e)*t1(m,a)) + end do + do f = 2*nocc+1, 2*nbasis + W_abef = 0.0_dp + W_abef = asym(a,b,e,f) + do n = 1, 2*nocc + W_abef = W_abef + t1(n,b)*asym(a,n,e,f) - t1(n,a)*asym(b,n,e,f) + end do + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(i,j,e,f)*W_abef + end do + end do + do m = 1, 2*nocc + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(i,m,a,b)*F_oo(m,j) + t2(j,m,a,b)*F_oo(m,i) & + - t1(m,a)*asym(m,b,i,j) + t1(m,b)*asym(m,a,i,j) + do e = 2*nocc+1, 2*nbasis + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*t1(j,e)-& + t2(j,m,a,b)*t1(i,e)) + end do + do n = 1, 2*nocc + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(m,n,a,b)*W_oooo(m,n,i,j) + end do + end do + + do m = 1, 2*nocc + do e = 2*nocc+1, 2*nbasis + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & + + t2(i,m,a,e)*W_ovvo(m,b,e,j) - t1(i,e)*t1(m,a)*asym(m,b,e,j)& + - t2(j,m,a,e)*W_ovvo(m,b,e,i) - t1(j,e)*t1(m,a)*asym(m,b,e,i)& + - t2(i,m,b,e)*W_ovvo(m,a,e,j) - t1(i,e)*t1(m,b)*asym(m,a,e,j)& + + t2(j,m,b,e)*W_ovvo(m,a,e,i) - t1(j,e)*t1(m,b)*asym(m,a,e,i) + end do + end do + end do + end do + end do + end do + t2 = tmp_t2/D_ijab + end associate + + end subroutine update_amplitudes + + subroutine update_cc_energy(sys, st, int_store, cc_amp) + use system, only: state_t + use integrals, only: int_store_t + + type(system_t), intent(in) :: sys + type(int_store_t), intent(in) :: int_store type(cc_amp_t), intent(in) :: cc_amp - real(p), intent(out) :: tau(:,:,:,:), tau_tilde(:,:,:,:) + type(state_t), intent(inout) :: st + + integer :: i, j, a, b + + st%energy_old = st%energy + st%energy = 0.0_p + associate(nocc=>sys%nocc, nbasis=>sys%nbasis, asym=>int_store%asym_spinorb, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab) + do i = 1, 2*nocc + do j = 1, 2*nocc + do a = 2*nocc+1, 2*nbasis + do b = 2*nocc+1, 2*nbasis + st%energy = st%energy + 0.25*asym(i,j,a,b)*(t2(i,j,a,b)+2*t1(i,a)*t1(j,b)) + end do + end do + end do + end do + end associate + + end subroutine update_cc_energy + + subroutine build_tau(sys, cc_amp, cc_int) + type(system_t), intent(in) :: sys + type(cc_amp_t), intent(in) :: cc_amp + type(cc_int_t), intent(inout) :: cc_int integer :: i, j, a, b real(p) :: ia, ja, x - associate(n=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) + associate(n=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& + tau=>cc_int%tau, tau_tilde=>cc_int%tau_tilde) do i = 1, 2*nocc do a = 2*nocc+1, 2*n ia = t_ia(i,a) @@ -164,17 +329,16 @@ subroutine build_tau(sys, cc_amp, tau, tau_tilde) end subroutine build_tau - subroutine build_F(sys, F_vv, F_oo, F_ov, cc_amp, asym, tau_tilde) + subroutine build_F(sys, cc_int, cc_amp, asym) ! Eqs. 3-5, as we use HF reference all terms involving the fock matrix vanishes type(system_t), intent(in) :: sys type(cc_amp_t), intent(in) :: cc_amp real(p), intent(in) :: asym(:,:,:,:) - real(p), intent(in) :: tau_tilde(:,:,:,:) - real(p), intent(out) :: F_vv(:,:), F_oo(:,:), F_ov(:,:) - + type(cc_int_t), intent(inout) :: cc_int integer :: a, e, f, m, n, i - associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& + F_vv=>cc_int%F_vv, F_oo=>cc_int%F_oo, F_ov=>cc_int%F_ov, tau_tilde=>cc_int%tau_tilde) ! F_ae = \sum_{mf} t_m^f * - 0.5 \sum_{mnf} \tau~_{mn}^{af} do a = 2*nocc+1, 2*nbasis do e = 2*nocc+1, 2*nbasis @@ -216,18 +380,17 @@ subroutine build_F(sys, F_vv, F_oo, F_ov, cc_amp, asym, tau_tilde) end associate end subroutine build_F - subroutine build_W(sys, W_oooo, W_ovvo, cc_amp, asym, tau) + subroutine build_W(sys, cc_int, cc_amp, asym) ! Eqs. 6 and 8 type(system_t), intent(in) :: sys type(cc_amp_t), intent(in) :: cc_amp real(p), intent(in) :: asym(:,:,:,:) - real(p), intent(in) :: tau(:,:,:,:) - real(p), intent(out) :: W_oooo(:,:,:,:), W_ovvo(:,:,:,:) - + type(cc_int_t), intent(inout) :: cc_int integer :: m, n, i, j, e, f, b real(p) :: x - associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& + W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau) do m = 1, 2*nocc do n = 1, 2*nocc do i = 1, 2*nocc @@ -253,7 +416,7 @@ subroutine build_W(sys, W_oooo, W_ovvo, cc_amp, asym, tau) W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) + t_ia(j,f)*asym(m,b,e,f) end do - do n = 1, 2*nbasis + do n = 1, 2*nocc x = t_ia(n,b) W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - x*asym(m,n,e,j) do f = 2*nocc+1, 2*nbasis From 61c342b79837e761c6856837a74db5bcf5fa5988 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sat, 25 Dec 2021 20:23:34 +0000 Subject: [PATCH 21/71] Milestone: working CCSD --- src/ccsd.f90 | 36 +++++++++++++++++++++--------------- 1 file changed, 21 insertions(+), 15 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 6700903..315cc88 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -98,12 +98,11 @@ subroutine do_ccsd(sys, int_store) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab, asym=>int_store%asym_spinorb) do iter = 1, maxiter ! Update intermediate tensors + call update_cc_energy(sys, st, int_store, cc_amp) call build_tau(sys, cc_amp, cc_int) call build_F(sys, cc_int, cc_amp, asym) call build_W(sys, cc_int, cc_amp, asym) - call update_amplitudes(sys, cc_amp, int_store, cc_int) - call update_cc_energy(sys, st, int_store, cc_amp) print*, st%energy end do end associate @@ -220,7 +219,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do end do end do - t1 = tmp_t1/D_ia + tmp_t1 = tmp_t1/D_ia ! Update T2 tmp_t2 = 0.0_dp @@ -231,26 +230,25 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) tmp_t2(i,j,a,b) = asym(i,j,a,b) do e = 2*nocc+1, 2*nbasis tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + t2(i,j,a,e)*F_vv(b,e) - t2(i,j,b,e)*F_vv(a,e) & - + t1(i,e)*asym(a,b,e,j) - t1(j,e)*asym(a,b,e,i) + + tmp_t1(i,e)*asym(a,b,e,j) - tmp_t1(j,e)*asym(a,b,e,i) do m = 1, 2*nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,j,a,e)*t1(m,b)-& - t2(i,j,b,e)*t1(m,a)) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,j,a,e)*tmp_t1(m,b)-& + t2(i,j,b,e)*tmp_t1(m,a)) end do do f = 2*nocc+1, 2*nbasis - W_abef = 0.0_dp W_abef = asym(a,b,e,f) do n = 1, 2*nocc - W_abef = W_abef + t1(n,b)*asym(a,n,e,f) - t1(n,a)*asym(b,n,e,f) + W_abef = W_abef - tmp_t1(n,b)*asym(a,n,e,f) + tmp_t1(n,a)*asym(b,n,e,f) end do tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(i,j,e,f)*W_abef end do end do do m = 1, 2*nocc tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(i,m,a,b)*F_oo(m,j) + t2(j,m,a,b)*F_oo(m,i) & - - t1(m,a)*asym(m,b,i,j) + t1(m,b)*asym(m,a,i,j) + - tmp_t1(m,a)*asym(m,b,i,j) + tmp_t1(m,b)*asym(m,a,i,j) do e = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*t1(j,e)-& - t2(j,m,a,b)*t1(i,e)) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*tmp_t1(j,e)-& + t2(j,m,a,b)*tmp_t1(i,e)) end do do n = 1, 2*nocc tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(m,n,a,b)*W_oooo(m,n,i,j) @@ -260,16 +258,17 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) do m = 1, 2*nocc do e = 2*nocc+1, 2*nbasis tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & - + t2(i,m,a,e)*W_ovvo(m,b,e,j) - t1(i,e)*t1(m,a)*asym(m,b,e,j)& - - t2(j,m,a,e)*W_ovvo(m,b,e,i) - t1(j,e)*t1(m,a)*asym(m,b,e,i)& - - t2(i,m,b,e)*W_ovvo(m,a,e,j) - t1(i,e)*t1(m,b)*asym(m,a,e,j)& - + t2(j,m,b,e)*W_ovvo(m,a,e,i) - t1(j,e)*t1(m,b)*asym(m,a,e,i) + + t2(i,m,a,e)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*asym(m,b,e,j)& + - t2(j,m,a,e)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*asym(m,b,e,i)& + - t2(i,m,b,e)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*asym(m,a,e,j)& + + t2(j,m,b,e)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*asym(m,a,e,i) end do end do end do end do end do end do + t1 = tmp_t1 t2 = tmp_t2/D_ijab end associate @@ -312,6 +311,8 @@ subroutine build_tau(sys, cc_amp, cc_int) associate(n=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& tau=>cc_int%tau, tau_tilde=>cc_int%tau_tilde) + tau = 0.0_p + tau_tilde = 0.0_p do i = 1, 2*nocc do a = 2*nocc+1, 2*n ia = t_ia(i,a) @@ -340,6 +341,9 @@ subroutine build_F(sys, cc_int, cc_amp, asym) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& F_vv=>cc_int%F_vv, F_oo=>cc_int%F_oo, F_ov=>cc_int%F_ov, tau_tilde=>cc_int%tau_tilde) ! F_ae = \sum_{mf} t_m^f * - 0.5 \sum_{mnf} \tau~_{mn}^{af} + F_vv = 0.0_p + F_oo = 0.0_p + F_ov = 0.0_p do a = 2*nocc+1, 2*nbasis do e = 2*nocc+1, 2*nbasis do m = 1, 2*nocc @@ -391,6 +395,8 @@ subroutine build_W(sys, cc_int, cc_amp, asym) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau) + W_oooo = 0.0_p + W_ovvo = 0.0_p do m = 1, 2*nocc do n = 1, 2*nocc do i = 1, 2*nocc From 0a3f7dcaac2ffd5a7fbf619827ffdbf5f4e5f599 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 26 Dec 2021 12:24:56 +0000 Subject: [PATCH 22/71] OMP parallelise Fock build code --- src/ccsd.f90 | 15 ++++++++++++--- src/hf.f90 | 5 +++++ src/main.F90 | 8 ++++---- 3 files changed, 21 insertions(+), 7 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 315cc88..3b39440 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -33,7 +33,7 @@ subroutine do_ccsd(sys, int_store) use error_handling, only: check_allocate use system, only: state_t - type(system_t), intent(in) :: sys + type(system_t), intent(inout) :: sys type(int_store_t), intent(inout) :: int_store integer :: i, j, a, b, p, q, r, s integer :: pr, qr, pa, pb, qa, qb, ra, rb, sa, sb @@ -95,18 +95,22 @@ subroutine do_ccsd(sys, int_store) call init_cc(sys, int_store, cc_amp, cc_int) + write(iunit, '(1X, A)') 'Initialisation done, now entering iterative CC solver...' + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab, asym=>int_store%asym_spinorb) do iter = 1, maxiter ! Update intermediate tensors call update_cc_energy(sys, st, int_store, cc_amp) + write(iunit, '(1X, A, 1X, I3, 1X, F15.8)') 'Iteration', iter, st%energy call build_tau(sys, cc_amp, cc_int) call build_F(sys, cc_int, cc_amp, asym) call build_W(sys, cc_int, cc_amp, asym) - call update_amplitudes(sys, cc_amp, int_store, cc_int) - print*, st%energy + call update_amplitudes(sys, cc_amp, int_store, cc_int) end do end associate + sys%e_ccsd = st%energy + end subroutine do_ccsd subroutine init_cc(sys, int_store, cc_amp, cc_int) @@ -119,7 +123,9 @@ subroutine init_cc(sys, int_store, cc_amp, cc_int) type(cc_int_t), intent(inout) :: cc_int integer :: p, q, r, s, i, j, a, b, ierr + integer, parameter :: iunit = 6 + write(iunit, '(1X, A)') 'Forming energy denominator matrices...' ! Forming the energy denominator matrices associate(n=>sys%nbasis, nocc=>sys%nocc, e=>sys%canon_levels) allocate(cc_int%D_ia(2*nocc, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) @@ -137,6 +143,7 @@ subroutine init_cc(sys, int_store, cc_amp, cc_int) end do end do + write(iunit, '(1X, A)') 'Allocating amplitude tensors...' ! Initialise t_i^a=0 and t_{ij}^{ab}=MP1 WF allocate(cc_amp%t_ijab(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) call check_allocate('cc_amp%t_ijab', 16*(nocc**2*(n-nocc)**2), ierr) @@ -148,6 +155,7 @@ subroutine init_cc(sys, int_store, cc_amp, cc_int) call check_allocate('cc_int%tmp_tia', 4*nocc*(n-nocc), ierr) end associate + write(iunit, '(1X, A)') 'Forming initial amplitude guesses...' associate(doubles=>cc_amp%t_ijab, nocc=>sys%nocc, asym=>int_store%asym_spinorb) do p = 1, 2*nocc do q = 1, 2*nocc @@ -160,6 +168,7 @@ subroutine init_cc(sys, int_store, cc_amp, cc_int) end do end associate + write(iunit, '(1X, A)') 'Allocating intermediate tensors...' ! Allocate the intermediate tensors associate(n=>sys%nbasis, nocc=>sys%nocc) allocate(cc_int%F_vv(2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) diff --git a/src/hf.f90 b/src/hf.f90 index 397f086..3e6908e 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -211,6 +211,10 @@ subroutine build_fock(sys, density, fock, int_store) integer :: ij, kl, ik, jl associate(eri=>int_store%eri) + !$omp parallel do default(none) & + !$omp schedule(dynamic, 2) collapse(2) & + !$omp private(ij, jl, kl, ik) & + !$omp shared(sys, density, fock, int_store) do j = 1, sys%nbasis do i = 1, sys%nbasis fock(i,j) = int_store%core_hamil(i,j) @@ -226,6 +230,7 @@ subroutine build_fock(sys, density, fock, int_store) end do end do end do + !$omp end parallel do end associate end subroutine build_fock diff --git a/src/main.F90 b/src/main.F90 index c3a8a28..0fbdebf 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -1,6 +1,7 @@ program main use const + use omp_lib use integrals, only: read_integrals_in, print_sys_info, int_store_t use system, only: system_t use hf, only: do_hartree_fock @@ -62,13 +63,12 @@ program main write(iunit, '(1X, A, 1X, F12.7)') 'E_CCSD: ', sys%e_ccsd write(iunit, '(1X, A, 1X, F12.7)') 'E_CCSD(T): ', sys%e_ccsd_t write(iunit, '(1X, 40("-"))') - write(iunit, '(1X, A, 1X, F12.7)') 'Total electronic energy:', sys%e_hf+sys%e_mp2+sys%e_ccsd+sys%e_ccsd_t - write(iunit, '(1X, A, 1X, F12.7)') 'Total energy: ', sys%e_hf+sys%e_mp2+sys%e_ccsd+sys%e_ccsd_t + int_store%e_nuc + write(iunit, '(1X, A, 1X, F12.7)') 'Total electronic energy:', sys%e_hf+sys%e_ccsd+sys%e_ccsd_t + write(iunit, '(1X, A, 1X, F12.7)') 'Total energy: ', sys%e_hf+sys%e_ccsd+sys%e_ccsd_t + int_store%e_nuc call date_and_time(VALUES=date_values) write(iunit, '(1X, 64("="))') write(iunit, '(1X, A, 1X, I2.2, "/", I2.2, "/", I4.4, 1X, A, 1X, I2.2, 2(":", I2.2))') & "Finished running on", date_values(3:1:-1), "at", date_values(5:7) - - + end program main \ No newline at end of file From 53a6cb9b97dd3193fe34c71486b65a13c3f139a0 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 26 Dec 2021 12:48:44 +0000 Subject: [PATCH 23/71] OMP parallelise MP2 --- src/mp2.f90 | 28 +++++++++++++++++++++++++--- 1 file changed, 25 insertions(+), 3 deletions(-) diff --git a/src/mp2.f90 b/src/mp2.f90 index 365344c..2c5bfc2 100644 --- a/src/mp2.f90 +++ b/src/mp2.f90 @@ -108,7 +108,12 @@ subroutine do_mp2(sys, int_store) allocate(int_store%eri_mo, mold=int_store%eri) + + !$omp parallel default(none) & + !$omp private(kl, ij, pq, rs, pqrs, s_up, ia, ja, jb, ib) & + !$omp shared(sys, int_store, tmp_a, tmp_b, nocc, n) associate(C=>sys%canon_coeff, eri_mo=>int_store%eri_mo, eri=>int_store%eri) + !$omp do schedule(dynamic, 2) collapse(2) ! (ij|kl) -> (pj|kl) do k = 1, n do l = 1, n @@ -123,7 +128,9 @@ subroutine do_mp2(sys, int_store) end do end do end do + !$omp end do + !$omp do schedule(dynamic, 2) collapse(2) ! (pj|kl) -> (pq|kl) do k = 1, n do l = 1, n @@ -137,10 +144,14 @@ subroutine do_mp2(sys, int_store) end do end do end do + !$omp end do ! (pq|kl) -> (pq|rl) + !$omp master tmp_a(:,:,:,:) = 0.0_dp - pq = 0 + !$omp end master + + !$omp do schedule(dynamic, 2) collapse(2) do p = 1, n do q = 1, n pq = eri_ind(p,q) @@ -154,10 +165,13 @@ subroutine do_mp2(sys, int_store) end do end do end do + !$omp end do ! (pq|rl) -> (pq|rs) + !$omp master tmp_b(:,:,:,:) = 0.0_dp - pq = 0 + !$omp end master + !$omp do schedule(dynamic, 2) collapse(2) do p = 1, n do q = 1, n pq = eri_ind(p,q) @@ -171,7 +185,9 @@ subroutine do_mp2(sys, int_store) end do end do end do + !$omp end do + !$omp master pq = 0 pqrs = 0 do p = 1, n @@ -192,13 +208,17 @@ subroutine do_mp2(sys, int_store) end do end do end do + !$omp end master end associate + !$omp end parallel - deallocate(tmp_a, tmp_b) + deallocate(tmp_a, tmp_b) write(iunit, '(1X, A)') 'Calculating MP2 energy...' + nocc = sys%nel/2 associate(e=>sys%canon_levels, eri=>int_store%eri_mo, emp=>sys%e_mp2) + emp = 0.0_dp do i = 1, nocc do j = 1, nocc do a = nocc+1, n @@ -214,6 +234,8 @@ subroutine do_mp2(sys, int_store) end do end do end associate + + write(iunit, '(1X, A, 1X, F15.8)') 'MP2 correlation energy (Hartree):', sys%e_mp2 end subroutine do_mp2 From 3ac324bb5f1be0640f7f7e392cbcc4a0ecbda207 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 26 Dec 2021 17:47:11 +0000 Subject: [PATCH 24/71] OMP parallelise CCSD --- src/ccsd.f90 | 43 ++++++++++++++++++++++++++++++++++++++++++- 1 file changed, 42 insertions(+), 1 deletion(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 3b39440..aa9304f 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -205,7 +205,14 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nbasis=>sys%nbasis) ! Update T1 + !$omp parallel default(none) & + !$omp private(i, j, a, b, m, n, e, f, W_abef) & + !$omp shared(sys, cc_amp, int_store, cc_int) + + !$omp master tmp_t1 = 0.0_dp + !$omp end master + !$omp do schedule(dynamic, 2) collapse(3) do i = 1, 2*nocc do a = 2*nocc+1, 2*nbasis do m = 1, 2*nocc @@ -228,10 +235,16 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do end do end do - tmp_t1 = tmp_t1/D_ia + !$omp end do + !$omp master + tmp_t1 = tmp_t1/D_ia + ! Update T2 tmp_t2 = 0.0_dp + !$omp end master + + !$omp do schedule(dynamic, 2) collapse(4) do i = 1, 2*nocc do j = 1, 2*nocc do a = 2*nocc+1, 2*nbasis @@ -277,6 +290,8 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do end do end do + !$omp end do + !$omp end parallel t1 = tmp_t1 t2 = tmp_t2/D_ijab end associate @@ -322,6 +337,10 @@ subroutine build_tau(sys, cc_amp, cc_int) tau=>cc_int%tau, tau_tilde=>cc_int%tau_tilde) tau = 0.0_p tau_tilde = 0.0_p + !$omp parallel do default(none) & + !$omp private(i,j,a,b,ia,ja,x) & + !$omp shared(sys, cc_amp, cc_int) & + !$omp schedule(dynamic, 2) collapse(2) do i = 1, 2*nocc do a = 2*nocc+1, 2*n ia = t_ia(i,a) @@ -335,6 +354,7 @@ subroutine build_tau(sys, cc_amp, cc_int) end do end do end do + !$omp end parallel do end associate end subroutine build_tau @@ -353,6 +373,12 @@ subroutine build_F(sys, cc_int, cc_amp, asym) F_vv = 0.0_p F_oo = 0.0_p F_ov = 0.0_p + + !$omp parallel default(none) & + !$omp private(a, e, f, m, n, i) & + !$omp shared(sys, cc_int, cc_amp, asym) + + !$omp do schedule(dynamic, 2) collapse(4) do a = 2*nocc+1, 2*nbasis do e = 2*nocc+1, 2*nbasis do m = 1, 2*nocc @@ -365,8 +391,10 @@ subroutine build_F(sys, cc_int, cc_amp, asym) end do end do end do + !$omp end do ! F_mi = \sum_{en} t_n^e + 0.5 \sum_{nef} \tau~_{in}^{ef} + !$omp do schedule(dynamic, 2) collapse(4) do m = 1, 2*nocc do i = 1, 2*nocc do e = 2*nocc+1, 2*nbasis @@ -379,8 +407,10 @@ subroutine build_F(sys, cc_int, cc_amp, asym) end do end do end do + !$omp end do ! F_me = \sum_{nf} t_n^f * + !$omp do schedule(dynamic, 2) collapse(4) do m = 1, 2*nocc do e = 2*nocc+1, 2*nbasis do n = 1, 2*nocc @@ -390,6 +420,8 @@ subroutine build_F(sys, cc_int, cc_amp, asym) end do end do end do + !$omp end do + !$omp end parallel end associate end subroutine build_F @@ -406,6 +438,11 @@ subroutine build_W(sys, cc_int, cc_amp, asym) W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau) W_oooo = 0.0_p W_ovvo = 0.0_p + !$omp parallel default(none) & + !$omp private(m, n, i, j, e, f, b, x) & + !$omp shared(sys, cc_int, cc_amp, asym) + + !$omp do schedule(dynamic, 2) collapse(4) do m = 1, 2*nocc do n = 1, 2*nocc do i = 1, 2*nocc @@ -421,7 +458,9 @@ subroutine build_W(sys, cc_int, cc_amp, asym) end do end do end do + !$omp end do + !$omp do schedule(dynamic, 2) collapse(4) do m = 1, 2*nocc do b = 2*nocc+1, 2*nbasis do e = 2*nocc+1, 2*nbasis @@ -442,6 +481,8 @@ subroutine build_W(sys, cc_int, cc_amp, asym) end do end do end do + !$omp end do + !$omp end parallel end associate end subroutine build_W From 1d294c0f3ed0bd4c8a2cfaeb64564467b921f9a2 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 26 Dec 2021 17:50:44 +0000 Subject: [PATCH 25/71] Update README.md --- README.md | 5 +++-- 1 file changed, 3 insertions(+), 2 deletions(-) diff --git a/README.md b/README.md index f6c56c5..41ffb08 100644 --- a/README.md +++ b/README.md @@ -9,10 +9,11 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [x] Hartree-Fock without symmetry - [x] Pretty printing, time reporting - [x] MP2 without symmetry -- [ ] CCSD without symmetry +- [X] CCSD without symmetry +- [X] OpenMP parallelisation - [ ] Adapting Hartree-Fock with symmetry - [ ] Ditto for MP2 - [ ] Ditto for CCSD - [ ] CCSD(T) with symmetry -- [ ] OpenMP / MPI parallelisation +- [ ] MPI parallelisation - [ ] GPU adaptation for MP2 and CCSD/(T) From 9f8151dcfa4ac19a0e1d4052cfae3c566b2a7023 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 26 Dec 2021 17:54:07 +0000 Subject: [PATCH 26/71] Update CMakeLists with OpenMP flags --- CMakeLists.txt | 4 ++-- 1 file changed, 2 insertions(+), 2 deletions(-) diff --git a/CMakeLists.txt b/CMakeLists.txt index 4bc497e..969ca64 100644 --- a/CMakeLists.txt +++ b/CMakeLists.txt @@ -7,11 +7,11 @@ project (els) enable_language (Fortran) if (CMAKE_Fortran_COMPILER_ID MATCHES "GNU") - set (dialect "-ffree-form -std=f2008 -fimplicit-none") + set (dialect "-ffree-form -std=f2008 -fimplicit-none -fopenmp") set (extras "-fcheck=all -ggdb") endif () if (CMAKE_Fortran_COMPILER_ID MATCHES "Intel") - set (dialect "-stand f08 -free -implicitnone") + set (dialect "-stand f08 -free -implicitnone -qopenmp") set (extras "-check bounds") endif () From 1766e200a09ae62dece04bdd0f58b040a5fc97a8 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 26 Dec 2021 18:08:49 +0000 Subject: [PATCH 27/71] Correct collapse clause behaviour --- src/ccsd.f90 | 8 ++++---- 1 file changed, 4 insertions(+), 4 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index aa9304f..d0a6cbb 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -212,7 +212,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) !$omp master tmp_t1 = 0.0_dp !$omp end master - !$omp do schedule(dynamic, 2) collapse(3) + !$omp do schedule(dynamic, 2) collapse(2) do i = 1, 2*nocc do a = 2*nocc+1, 2*nbasis do m = 1, 2*nocc @@ -378,7 +378,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp private(a, e, f, m, n, i) & !$omp shared(sys, cc_int, cc_amp, asym) - !$omp do schedule(dynamic, 2) collapse(4) + !$omp do schedule(dynamic, 2) collapse(2) do a = 2*nocc+1, 2*nbasis do e = 2*nocc+1, 2*nbasis do m = 1, 2*nocc @@ -394,7 +394,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp end do ! F_mi = \sum_{en} t_n^e + 0.5 \sum_{nef} \tau~_{in}^{ef} - !$omp do schedule(dynamic, 2) collapse(4) + !$omp do schedule(dynamic, 2) collapse(2) do m = 1, 2*nocc do i = 1, 2*nocc do e = 2*nocc+1, 2*nbasis @@ -410,7 +410,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp end do ! F_me = \sum_{nf} t_n^f * - !$omp do schedule(dynamic, 2) collapse(4) + !$omp do schedule(dynamic, 2) collapse(2) do m = 1, 2*nocc do e = 2*nocc+1, 2*nbasis do n = 1, 2*nocc From 7486675fdf5686cfde35171e4c5aef54a83416f3 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 27 Dec 2021 17:15:29 +0000 Subject: [PATCH 28/71] Working DIIS for HF --- src/hf.f90 | 75 ++++++++++++++++++++++++++++++++++++++++++++------ src/linalg.f90 | 22 ++++++++++++++- 2 files changed, 87 insertions(+), 10 deletions(-) diff --git a/src/hf.f90 b/src/hf.f90 index 3e6908e..de817a2 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -3,6 +3,18 @@ module hf implicit none + type diis_t + ! Contains matrices for use in the DIIS procedure + integer :: n_errmat = 6 + integer :: n_active = 0 + integer :: iter = 0 + real(p), allocatable :: e(:,:,:) + real(p), allocatable :: F(:,:,:) + real(p), allocatable :: B(:,:) + real(p), allocatable :: c(:) + real(p), allocatable :: rhs(:) + end type diis_t + contains subroutine do_hartree_fock(sys, int_store) use error_handling @@ -21,8 +33,9 @@ subroutine do_hartree_fock(sys, int_store) real(p) :: tmpmat(sys%nbasis,sys%nbasis) type(state_t) :: st - integer :: iter, maxiter, iunit, i + integer :: iter, maxiter, iunit, i, j, ierr logical :: conv = .false. + type(diis_t) :: diis iunit = 6 maxiter = 100 @@ -40,9 +53,7 @@ subroutine do_hartree_fock(sys, int_store) ! S^(-1/2) = C * L^(-1/2) * C^(T) call diagonalise(ovlp) - !call zero_mat(ovlp%A) call build_ortmat(ovlp, ortmat) - !call zero_mat(ortmat) call deallocate_mat_t(ovlp) @@ -50,18 +61,17 @@ subroutine do_hartree_fock(sys, int_store) ! F'_0 = S^T(-1/2) * F * S^(-1/2) call init_mat_t(int_store%core_hamil, fockmat) + call init_diis_t(sys, diis) + do iter = 1, maxiter fockmat%ao_ort = matmul(transpose(ortmat), matmul(fockmat%ao, ortmat)) - !call zero_mat(fockmat%ao_ort) call diagonalise(fockmat) ! Transform coefficient into nonorthogonal AO basis fockmat%A = transpose(matmul(ortmat, fockmat%A)) - !call zero_mat(fockmat%A) call build_density(fockmat%A, density, sys%nel/2) - !call zero_mat(density) call update_scf_energy(density, fockmat%ao, st, int_store, conv) if (conv) then @@ -77,12 +87,47 @@ subroutine do_hartree_fock(sys, int_store) allocate(sys%canon_coeff, source=fockmat%A) allocate(sys%canon_levels, source=fockmat%W) exit - else - write(iunit, '(1X, A, 1X, I3, F15.8)') 'Iteration', iter, st%energy end if + write(iunit, '(1X, A, 1X, I3, F15.8)') 'Iteration', iter, st%energy call build_fock(sys, density, fockmat%ao, int_store) - !call zero_mat(fockmat%ao) + + ! DIIS update + !call update_diis(diis, fockmat%ao, density, int_store%ovlp) + diis%iter = diis%iter+1 + if (diis%iter > 6) diis%iter = diis%iter - 6 + if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 + diis%F(diis%iter,:,:) = 0.0_p + diis%e(diis%iter,:,:) = 0.0_p + diis%F(diis%iter,:,:) = fockmat%ao(:,:) + diis%e(diis%iter,:,:) = matmul(fockmat%ao, matmul(density,int_store%ovlp)) & + - matmul(int_store%ovlp, matmul(density, fockmat%ao)) + + associate(n=>diis%n_active, nerr=>diis%n_errmat) + if (n > 1) then + ! Construct the B matrix + if (n <= nerr) then + if (allocated(diis%B)) deallocate(diis%B, diis%c, diis%rhs) + allocate(diis%B(n+1,n+1), diis%c(n+1), diis%rhs(n+1), source=0.0_p) + end if + diis%B(n+1,:) = -1.0_p + diis%B(n+1,n+1) = 0.0_p + diis%rhs(n+1) = -1.0_p + diis%c = diis%rhs + do i = 1, n + do j = 1, i + diis%B(i,j) = sum(diis%e(i,:,:)*diis%e(j,:,:)) + end do + end do + call linsolve(diis%B, diis%c, ierr) + if (ierr /= 0) call error('hf::linsolve', 'Linear solve failed!') + fockmat%ao = 0.0_p + do i = 1, n + fockmat%ao = fockmat%ao + diis%c(i) * diis%F(i,:,:) + end do + end if + end associate + end do if (.not. conv) then @@ -91,6 +136,18 @@ subroutine do_hartree_fock(sys, int_store) end subroutine do_hartree_fock + subroutine init_diis_t(sys, diis) + use system, only: system_t + + type(system_t), intent(in) :: sys + type(diis_t), intent(out) :: diis + + associate(n=>sys%nbasis) + allocate(diis%e(diis%n_errmat,n,n), source=0.0_p) + allocate(diis%F(diis%n_errmat,n,n), source=0.0_p) + end associate + end subroutine init_diis_t + subroutine diagonalise(mat) ! For a symmetric matrix A we produce ! A = C * L * C^T diff --git a/src/linalg.f90 b/src/linalg.f90 index bc16e60..9085ef2 100644 --- a/src/linalg.f90 +++ b/src/linalg.f90 @@ -30,11 +30,31 @@ subroutine eigs(mat, ierr) do i = 1, 2 allocate(work(abs(lwork))) call dsyev('V', 'U', mat%N, mat%A(:,:), mat%N, mat%W, work, lwork, ierr) - lwork = ceiling(work(1)) ! nint used in HANDE + lwork = nint(work(1)) deallocate(work) end do end subroutine eigs + subroutine linsolve(A, B, ierr) + real(p), intent(inout) :: A(:,:) + real(p), intent(inout) :: B(:) + integer, intent(out) :: ierr + + real(p), allocatable :: work(:) + real(p), allocatable :: ipiv(:) + integer :: lwork, i + + lwork = -1 + allocate(ipiv(size(B))) + do i = 1, 2 + allocate(work(abs(lwork))) + call dsysv('L', size(B), 1, A, size(B), ipiv, B, size(B), work, lwork, ierr) + lwork = nint(work(1)) + deallocate(work) + end do + + end subroutine linsolve + elemental subroutine zero_mat(matel) ! Zero out entries smaller than machine precision From 7bf328a6823623dd0b4856c912c91932e6a8ed29 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 27 Dec 2021 17:16:26 +0000 Subject: [PATCH 29/71] Update README.md --- README.md | 2 ++ 1 file changed, 2 insertions(+) diff --git a/README.md b/README.md index 41ffb08..ea2df9e 100644 --- a/README.md +++ b/README.md @@ -11,6 +11,8 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [x] MP2 without symmetry - [X] CCSD without symmetry - [X] OpenMP parallelisation +- [X] DIIS acceleration for Hartree-Fock SCF +- [ ] DIIS acceleration for CCSD iterations - [ ] Adapting Hartree-Fock with symmetry - [ ] Ditto for MP2 - [ ] Ditto for CCSD From f295c4f447196b16fed7648f0d3f32d8119ef410 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 27 Dec 2021 20:21:48 +0000 Subject: [PATCH 30/71] Add deallocation of data types, further OMP, convergence checking in CCSD --- src/ccsd.f90 | 89 +++++++++++++++++++++++++++++++++++---------- src/hf.f90 | 97 +++++++++++++++++++++++++++++--------------------- src/mp2.f90 | 1 - src/system.f90 | 6 +++- 4 files changed, 133 insertions(+), 60 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index d0a6cbb..62af0aa 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -15,7 +15,7 @@ module ccsd ! Curly F tensors (Eqs. 3-5) real(dp), allocatable :: F_oo(:,:), F_vv(:,:), F_ov(:,:) ! Curly W tensors (Eqs. 6,8), see Appendix for why 7 is avoided - real(dp), allocatable :: W_oooo(:,:,:,:), W_ovvo(:,:,:,:) + real(dp), allocatable :: W_oooo(:,:,:,:), W_vvvv(:,:,:,:), W_ovvo(:,:,:,:) ! Effective two-particle excitation operators tau and tilde tau (Eqs. 9-10) real(dp), allocatable :: tau_tilde(:,:,:,:), tau(:,:,:,:) ! Energy denominators (Eqs. 12-13) @@ -47,6 +47,7 @@ subroutine do_ccsd(sys, int_store) integer, parameter :: maxiter = 50 type(cc_int_t) :: cc_int + logical :: conv write(iunit, '(1X, 10("-"))') write(iunit, '(1X, A)') 'CCSD' @@ -94,22 +95,35 @@ subroutine do_ccsd(sys, int_store) end associate call init_cc(sys, int_store, cc_amp, cc_int) + allocate(st%t2_old, source=cc_amp%t_ijab) write(iunit, '(1X, A)') 'Initialisation done, now entering iterative CC solver...' associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab, asym=>int_store%asym_spinorb) do iter = 1, maxiter ! Update intermediate tensors - call update_cc_energy(sys, st, int_store, cc_amp) - write(iunit, '(1X, A, 1X, I3, 1X, F15.8)') 'Iteration', iter, st%energy call build_tau(sys, cc_amp, cc_int) call build_F(sys, cc_int, cc_amp, asym) call build_W(sys, cc_int, cc_amp, asym) + call update_amplitudes(sys, cc_amp, int_store, cc_int) + call update_cc_energy(sys, st, int_store, cc_amp, conv) + if (conv) then + write(iunit, '(1X, A)') 'Convergence reached within tolerance.' + write(iunit, '(1X, A, 1X, F15.8)') 'Final CCSD Energy (Hartree):', st%energy + + ! Copied for return + sys%e_ccsd = st%energy + call move_alloc(cc_amp%t_ia, sys%t1) + call move_alloc(cc_amp%t_ijab, sys%t2) + exit + end if + write(iunit, '(1X, A, 1X, I3, 1X, F15.8)') 'Iteration', iter, st%energy end do end associate - sys%e_ccsd = st%energy + deallocate(st%t2_old) + call deallocate_cc_int_t(cc_int) end subroutine do_ccsd @@ -179,6 +193,8 @@ subroutine init_cc(sys, int_store, cc_amp, cc_int) call check_allocate('cc_int%F_ov', 4*nocc*(n-nocc), ierr) allocate(cc_int%W_oooo(2*nocc,2*nocc,2*nocc,2*nocc), source=0.0_dp, stat=ierr) call check_allocate('cc_int%W_oooo', 16*nocc**4, ierr) + allocate(cc_int%W_vvvv(2*nocc+1:2*n,2*nocc+1:2*n,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%W_vvvv', 16*(n-nocc)**4, ierr) allocate(cc_int%W_ovvo(2*nocc,2*nocc+1:2*n,2*nocc+1:2*n,2*nocc), source=0.0_dp, stat=ierr) call check_allocate('cc_int%W_ovvo', 16*nocc**2*(n-nocc)**2, ierr) allocate(cc_int%tau(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) @@ -189,6 +205,17 @@ subroutine init_cc(sys, int_store, cc_amp, cc_int) end subroutine init_cc + subroutine deallocate_cc_int_t(cc_int) + type(cc_int_t), intent(inout) :: cc_int + + deallocate(cc_int%F_oo, cc_int%F_vv, cc_int%F_ov) + deallocate(cc_int%W_oooo, cc_int%W_vvvv, cc_int%W_ovvo) + deallocate(cc_int%tau, cc_int%tau_tilde) + deallocate(cc_int%D_ia, cc_int%D_ijab) + deallocate(cc_int%tmp_tia, cc_int%tmp_tijab) + end subroutine + + subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) use integrals, only: int_store_t @@ -198,15 +225,15 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) type(cc_int_t), intent(inout) :: cc_int integer :: i, j, a, b, m, n, e, f - real(p) :: W_abef associate(tmp_t1=>cc_int%tmp_tia,tmp_t2=>cc_int%tmp_tijab,t1=>cc_amp%t_ia,t2=>cc_amp%t_ijab,asym=>int_store%asym_spinorb, & F_oo=>cc_int%F_oo,F_ov=>cc_int%F_ov,F_vv=>cc_int%F_vv,D_ia=>cc_int%D_ia,D_ijab=>cc_int%D_ijab,W_oooo=>cc_int%W_oooo, & - W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nbasis=>sys%nbasis) + W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nbasis=>sys%nbasis,& + W_vvvv=>cc_int%W_vvvv) ! Update T1 !$omp parallel default(none) & - !$omp private(i, j, a, b, m, n, e, f, W_abef) & + !$omp private(i, j, a, b, m, n, e, f) & !$omp shared(sys, cc_amp, int_store, cc_int) !$omp master @@ -258,11 +285,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) t2(i,j,b,e)*tmp_t1(m,a)) end do do f = 2*nocc+1, 2*nbasis - W_abef = asym(a,b,e,f) - do n = 1, 2*nocc - W_abef = W_abef - tmp_t1(n,b)*asym(a,n,e,f) + tmp_t1(n,a)*asym(b,n,e,f) - end do - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(i,j,e,f)*W_abef + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(i,j,e,f)*W_vvvv(a,b,e,f) end do end do do m = 1, 2*nocc @@ -298,7 +321,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end subroutine update_amplitudes - subroutine update_cc_energy(sys, st, int_store, cc_amp) + subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) use system, only: state_t use integrals, only: int_store_t @@ -306,21 +329,36 @@ subroutine update_cc_energy(sys, st, int_store, cc_amp) type(int_store_t), intent(in) :: int_store type(cc_amp_t), intent(in) :: cc_amp type(state_t), intent(inout) :: st + logical, intent(out) :: conv integer :: i, j, a, b + real(p) :: ecc, rmst2 + conv = .false. st%energy_old = st%energy - st%energy = 0.0_p associate(nocc=>sys%nocc, nbasis=>sys%nbasis, asym=>int_store%asym_spinorb, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab) + !$omp parallel default(none) & + !$omp private(i,j,a,b) & + !$omp shared(sys,st,int_store,cc_amp,ecc,rmst2) + ecc = 0.0_p + rmst2 = 0.0_p + !$omp do schedule(dynamic, 2) collapse(4) reduction(+:ecc,rmst2) do i = 1, 2*nocc do j = 1, 2*nocc do a = 2*nocc+1, 2*nbasis do b = 2*nocc+1, 2*nbasis - st%energy = st%energy + 0.25*asym(i,j,a,b)*(t2(i,j,a,b)+2*t1(i,a)*t1(j,b)) + ecc = ecc + 0.25*asym(i,j,a,b)*(t2(i,j,a,b)+2*t1(i,a)*t1(j,b)) + rmst2 = rmst2 + (t2(i,j,a,b)-st%t2_old(i,j,a,b))**2 end do end do end do end do + !$omp end do + !$omp end parallel + st%energy = ecc + st%t2_old = t2 + if (sqrt(rmst2) < 1e-5 .and. abs(st%energy-st%energy_old) < 1e-5) conv = .true. + end associate end subroutine update_cc_energy @@ -431,15 +469,15 @@ subroutine build_W(sys, cc_int, cc_amp, asym) type(cc_amp_t), intent(in) :: cc_amp real(p), intent(in) :: asym(:,:,:,:) type(cc_int_t), intent(inout) :: cc_int - integer :: m, n, i, j, e, f, b + integer :: m, n, i, j, e, f, b, a real(p) :: x associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& - W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau) + W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau, W_vvvv=>cc_int%W_vvvv) W_oooo = 0.0_p W_ovvo = 0.0_p !$omp parallel default(none) & - !$omp private(m, n, i, j, e, f, b, x) & + !$omp private(m, n, i, j, e, f, b, x, a) & !$omp shared(sys, cc_int, cc_amp, asym) !$omp do schedule(dynamic, 2) collapse(4) @@ -460,6 +498,21 @@ subroutine build_W(sys, cc_int, cc_amp, asym) end do !$omp end do + !$omp do schedule(dynamic, 2) collapse(4) + do a = 2*nocc+1, 2*nbasis + do b = 2*nocc+1, 2*nbasis + do e = 2*nocc+1, 2*nbasis + do f = 2*nocc+1, 2*nbasis + W_vvvv(a,b,e,f) = asym(a,b,e,f) + do n = 1, 2*nocc + W_vvvv(a,b,e,f) = W_vvvv(a,b,e,f) - t_ia(n,b)*asym(a,n,e,f) + t_ia(n,a)*asym(b,n,e,f) + end do + end do + end do + end do + end do + !$omp end do + !$omp do schedule(dynamic, 2) collapse(4) do m = 1, 2*nocc do b = 2*nocc+1, 2*nbasis diff --git a/src/hf.f90 b/src/hf.f90 index de817a2..99832be 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -43,7 +43,6 @@ subroutine do_hartree_fock(sys, int_store) write(iunit, '(1X, A)') 'Hartree-Fock' write(iunit, '(1X, 12("-"))') - allocate(st%density(sys%nbasis,sys%nbasis), source=0.0_p) allocate(st%density_old(sys%nbasis,sys%nbasis), source=0.0_p) ! Build the orthogonalisation matrix S^-1/2 @@ -93,49 +92,63 @@ subroutine do_hartree_fock(sys, int_store) call build_fock(sys, density, fockmat%ao, int_store) ! DIIS update - !call update_diis(diis, fockmat%ao, density, int_store%ovlp) - diis%iter = diis%iter+1 - if (diis%iter > 6) diis%iter = diis%iter - 6 - if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 - diis%F(diis%iter,:,:) = 0.0_p - diis%e(diis%iter,:,:) = 0.0_p - diis%F(diis%iter,:,:) = fockmat%ao(:,:) - diis%e(diis%iter,:,:) = matmul(fockmat%ao, matmul(density,int_store%ovlp)) & - - matmul(int_store%ovlp, matmul(density, fockmat%ao)) - - associate(n=>diis%n_active, nerr=>diis%n_errmat) - if (n > 1) then - ! Construct the B matrix - if (n <= nerr) then - if (allocated(diis%B)) deallocate(diis%B, diis%c, diis%rhs) - allocate(diis%B(n+1,n+1), diis%c(n+1), diis%rhs(n+1), source=0.0_p) - end if - diis%B(n+1,:) = -1.0_p - diis%B(n+1,n+1) = 0.0_p - diis%rhs(n+1) = -1.0_p - diis%c = diis%rhs - do i = 1, n - do j = 1, i - diis%B(i,j) = sum(diis%e(i,:,:)*diis%e(j,:,:)) - end do - end do - call linsolve(diis%B, diis%c, ierr) - if (ierr /= 0) call error('hf::linsolve', 'Linear solve failed!') - fockmat%ao = 0.0_p - do i = 1, n - fockmat%ao = fockmat%ao + diis%c(i) * diis%F(i,:,:) - end do - end if - end associate - + call update_diis(diis, fockmat%ao, density, int_store%ovlp) end do if (.not. conv) then write(iunit, '(1X, A)') 'Convergence not reached, please increase maxiter.' end if + call deallocate_diis_t(diis) + deallocate(st%density_old) + end subroutine do_hartree_fock + subroutine update_diis(diis, fock, density, ovlp) + use linalg, only: linsolve + use error_handling, only: error + + type(diis_t), intent(inout) :: diis + real(p), intent(inout) :: fock(:,:) + real(p), intent(in) :: ovlp(:,:), density(:,:) + + integer :: i, j, ierr + + diis%iter = diis%iter+1 + if (diis%iter > 6) diis%iter = diis%iter - 6 + if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 + diis%F(diis%iter,:,:) = 0.0_p + diis%e(diis%iter,:,:) = 0.0_p + diis%F(diis%iter,:,:) = fock(:,:) + diis%e(diis%iter,:,:) = matmul(fock, matmul(density,ovlp)) & + - matmul(ovlp, matmul(density, fock)) + + associate(n=>diis%n_active, nerr=>diis%n_errmat) + if (n > 1) then + ! Construct the B matrix + if (n <= nerr) then + if (allocated(diis%B)) deallocate(diis%B, diis%c, diis%rhs) + allocate(diis%B(n+1,n+1), diis%c(n+1), diis%rhs(n+1), source=0.0_p) + end if + diis%B(n+1,:) = -1.0_p + diis%B(n+1,n+1) = 0.0_p + diis%rhs(n+1) = -1.0_p + diis%c = diis%rhs + do i = 1, n + do j = 1, i + diis%B(i,j) = sum(diis%e(i,:,:)*diis%e(j,:,:)) + end do + end do + call linsolve(diis%B, diis%c, ierr) + if (ierr /= 0) call error('hf::update_diis', 'Linear solve failed!') + fock = 0.0_p + do i = 1, n + fock = fock + diis%c(i) * diis%F(i,:,:) + end do + end if + end associate + end subroutine update_diis + subroutine init_diis_t(sys, diis) use system, only: system_t @@ -148,6 +161,12 @@ subroutine init_diis_t(sys, diis) end associate end subroutine init_diis_t + subroutine deallocate_diis_t(diis) + type(diis_t), intent(inout) :: diis + + deallocate(diis%e, diis%F, diis%B, diis%c, diis%rhs) + end subroutine deallocate_diis_t + subroutine diagonalise(mat) ! For a symmetric matrix A we produce ! A = C * L * C^T @@ -244,13 +263,11 @@ subroutine update_scf_energy(density, fock, st, int_store, conv) type(state_t), intent(inout) :: st logical, intent(inout) :: conv - st%density_old = st%density - st%density = density - st%energy_old = st%energy st%energy = sum(density * (int_store%core_hamil + fock)) - if (sqrt(sum((density-st%density_old)**2)) < 1e-5 .and. abs(st%energy-st%energy_old) < 1e-5) conv = .true. + if (sqrt(sum((density-st%density_old)**2)) < 1e-7 .and. abs(st%energy-st%energy_old) < 1e-7) conv = .true. + st%density_old = density end subroutine update_scf_energy diff --git a/src/mp2.f90 b/src/mp2.f90 index 2c5bfc2..0b71fd1 100644 --- a/src/mp2.f90 +++ b/src/mp2.f90 @@ -234,7 +234,6 @@ subroutine do_mp2(sys, int_store) end do end do end associate - write(iunit, '(1X, A, 1X, F15.8)') 'MP2 correlation energy (Hartree):', sys%e_mp2 diff --git a/src/system.f90 b/src/system.f90 index 583da2c..e514203 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -23,6 +23,10 @@ module system real(p), allocatable :: canon_coeff(:,:) real(p), allocatable :: canon_levels(:) + ! Converged CCSD amplitudes + real(p), allocatable :: t1(:,:) + real(p), allocatable :: t2(:,:,:,:) + end type system_t @@ -31,8 +35,8 @@ module system integer :: iter = 0 real(p) :: energy = 0.0_p real(p) :: energy_old = 0.0_p - real(p), allocatable :: density(:,:) real(p), allocatable :: density_old(:,:) + real(p), allocatable :: t2_old(:,:,:,:) end type state_t end module system \ No newline at end of file From 1456ebda04dce688f89af09a9c976be67499d6fd Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 27 Dec 2021 22:50:26 +0000 Subject: [PATCH 31/71] Update README.md --- README.md | 7 +++++-- 1 file changed, 5 insertions(+), 2 deletions(-) diff --git a/README.md b/README.md index ea2df9e..cf0074c 100644 --- a/README.md +++ b/README.md @@ -2,7 +2,7 @@ This project is based on the Crawford Group's excellent [C++ Programming Tutorial in Chemistry](https://github.com/CrawfordGroup/ProgrammingProjects), but written in Fortran. The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as per the original tutorial, but with additional support for multicore processors (modern CPUs, GPUs). -## Progress +## Progress / to-do - [x] Geometry read-in - [x] Integral read-in - [x] Nuclear repulsion energy calculation @@ -13,9 +13,12 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [X] OpenMP parallelisation - [X] DIIS acceleration for Hartree-Fock SCF - [ ] DIIS acceleration for CCSD iterations +- [ ] Loop optimisations (fusing triangular loops, cache optimisations) +- [ ] CCSD(T) without symmetry +- [ ] Looping optimisation / fusing trian - [ ] Adapting Hartree-Fock with symmetry - [ ] Ditto for MP2 - [ ] Ditto for CCSD -- [ ] CCSD(T) with symmetry +- [ ] Ditto for CCSD(T) - [ ] MPI parallelisation - [ ] GPU adaptation for MP2 and CCSD/(T) From 4e2fe735ad463b15b88260136b4116edd88e6064 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 27 Dec 2021 22:57:45 +0000 Subject: [PATCH 32/71] Update README.md --- README.md | 1 - 1 file changed, 1 deletion(-) diff --git a/README.md b/README.md index cf0074c..a43990d 100644 --- a/README.md +++ b/README.md @@ -15,7 +15,6 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [ ] DIIS acceleration for CCSD iterations - [ ] Loop optimisations (fusing triangular loops, cache optimisations) - [ ] CCSD(T) without symmetry -- [ ] Looping optimisation / fusing trian - [ ] Adapting Hartree-Fock with symmetry - [ ] Ditto for MP2 - [ ] Ditto for CCSD From cc4b67e4dbf34f3bba3927200ef15f382b5cccd4 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Tue, 28 Dec 2021 14:07:02 +0000 Subject: [PATCH 33/71] Working CCSD(T) --- dat/enuc.dat | 1 - dat/eri.dat | 228 ------------------------------------------------- dat/geom.dat | 4 - dat/input.dat | 12 --- dat/mux.dat | 28 ------ dat/muy.dat | 28 ------ dat/muz.dat | 28 ------ dat/s.dat | 28 ------ dat/t.dat | 28 ------ dat/v.dat | 28 ------ els.x | Bin 422264 -> 0 bytes src/ccsd.f90 | 77 ++++++++++++++++- src/main.F90 | 16 ++-- src/system.f90 | 1 + 14 files changed, 88 insertions(+), 419 deletions(-) delete mode 100644 dat/enuc.dat delete mode 100644 dat/eri.dat delete mode 100644 dat/geom.dat delete mode 100644 dat/input.dat delete mode 100644 dat/mux.dat delete mode 100644 dat/muy.dat delete mode 100644 dat/muz.dat delete mode 100644 dat/s.dat delete mode 100644 dat/t.dat delete mode 100644 dat/v.dat delete mode 100644 els.x diff --git a/dat/enuc.dat b/dat/enuc.dat deleted file mode 100644 index 6b08fe4..0000000 --- a/dat/enuc.dat +++ /dev/null @@ -1 +0,0 @@ - 8.002367061810450 diff --git a/dat/eri.dat b/dat/eri.dat deleted file mode 100644 index 5351060..0000000 --- a/dat/eri.dat +++ /dev/null @@ -1,228 +0,0 @@ - 1 1 1 1 4.785065404705506 - 2 1 1 1 0.741380351973408 - 2 2 1 1 1.118946866342470 - 2 1 2 1 0.136873385354388 - 2 2 2 1 0.256633394730974 - 2 2 2 2 0.817206321526058 - 3 3 1 1 1.115813812152428 - 4 4 1 1 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Initialise t_i^a=0 and t_{ij}^{ab}=MP1 WF allocate(cc_amp%t_ijab(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) @@ -540,4 +545,74 @@ subroutine build_W(sys, cc_int, cc_amp, asym) end associate end subroutine build_W + subroutine do_ccsd_t(sys, int_store) + use integrals, only: int_store_t + use error_handling, only: check_allocate + + type(system_t), intent(inout) :: sys + type(int_store_t), intent(in) :: int_store + + integer :: i, j, k, a, b, c, f, m, ierr + real(p), allocatable :: tmp_t3d(:,:,:), tmp_t3c(:,:,:), tmp_t3c_d(:,:,:) + real(p) :: e_T + + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, e=>sys%canon_levels_spinorb, t1=>sys%t1, t2=>sys%t2,& + asym=>int_store%asym_spinorb) + !$omp parallel default(none) & + !$omp private(i, j, k, a, b, c, f, m, tmp_t3d, tmp_t3c, tmp_t3c_d, ierr) & + !$omp shared(sys, int_store, e_T) + e_T = 0.0_p + + ! Declare heap-allocated arrays inside parallel region + allocate(tmp_t3d(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) + call check_allocate('tmp_t3d', 8*(nbasis-nocc)**3, ierr) + allocate(tmp_t3c(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) + call check_allocate('tmp_t3c', 8*(nbasis-nocc)**3, ierr) + allocate(tmp_t3c_d(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) + call check_allocate('tmp_t3c_d', 8*(nbasis-nocc)**3, ierr) + + !$omp do schedule(dynamic, 2) collapse(3) reduction(+:e_T) + do i = 1, 2*nocc + do j = 1, 2*nocc + do k = 1, 2*nocc + ! Compute T3 amplitudes + do a = 2*nocc+1, 2*nbasis + do b = 2*nocc+1, 2*nbasis + do c = 2*nocc+1, 2*nbasis + ! Disonnected T3: t_{ijk}^{abc}(d) = P(i/jk)P(a/bc)t_i^a* + tmp_t3d(a,b,c) = t1(i,a)*asym(j,k,b,c) - t1(j,a)*asym(i,k,b,c) - t1(k,a)*asym(j,i,b,c) & + - t1(i,b)*asym(j,k,a,c) + t1(j,b)*asym(i,k,a,c) + t1(k,b)*asym(j,i,a,c) & + - t1(i,c)*asym(j,k,b,a) + t1(j,c)*asym(i,k,b,a) + t1(k,c)*asym(j,i,b,a) + tmp_t3d(a,b,c) = tmp_t3d(a,b,c)/(e(i)+e(j)+e(k)-e(a)-e(b)-e(c)) + ! Conneccted T3: t_{ijk}^{abc}(c) = P(i/jk)P(a/bc)[\sum_f t_jk^af - \sum_m t_im^bc ] + + tmp_t3c(a,b,c) = 0.0_p + do f = 2*nocc+1, 2*nbasis + tmp_t3c(a,b,c) = tmp_t3c(a,b,c) & + + t2(j,k,a,f)*asym(f,i,b,c) - t2(i,k,a,f)*asym(f,j,b,c) - t2(j,i,a,f)*asym(f,k,b,c) & + - t2(j,k,b,f)*asym(f,i,a,c) + t2(i,k,b,f)*asym(f,j,a,c) + t2(j,i,b,f)*asym(f,k,a,c) & + - t2(j,k,c,f)*asym(f,i,b,a) + t2(i,k,c,f)*asym(f,j,b,a) + t2(j,i,c,f)*asym(f,k,b,a) + end do + do m = 1, 2*nocc + tmp_t3c(a,b,c) = tmp_t3c(a,b,c) & + - t2(i,m,b,c)*asym(m,a,j,k) + t2(j,m,b,c)*asym(m,a,i,k) + t2(k,m,b,c)*asym(m,a,j,i) & + + t2(i,m,a,c)*asym(m,b,j,k) - t2(j,m,a,c)*asym(m,b,i,k) - t2(k,m,a,c)*asym(m,b,j,i) & + + t2(i,m,b,a)*asym(m,c,j,k) - t2(j,m,b,a)*asym(m,c,i,k) - t2(k,m,b,a)*asym(m,c,j,i) + end do + tmp_t3c_d(a,b,c) = tmp_t3c(a,b,c)/(e(i)+e(j)+e(k)-e(a)-e(b)-e(c)) + end do + end do + end do + + ! Calculate contributions + e_T = e_T + sum(tmp_t3c*(tmp_t3c_d+tmp_t3d))/36 + end do + end do + end do + !$omp end do + !$omp end parallel + print*, e_T + end associate + end subroutine do_ccsd_t + end module ccsd \ No newline at end of file diff --git a/src/main.F90 b/src/main.F90 index 0fbdebf..4eb2f72 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -7,7 +7,7 @@ program main use hf, only: do_hartree_fock use geometry, only: read_geometry_in use mp2, only: do_mp2 - use ccsd, only: do_ccsd + use ccsd, only: do_ccsd, do_ccsd_t implicit none @@ -35,25 +35,31 @@ program main call print_sys_info(sys, int_store) call system_clock(t1) if (t1 = - ! where = (pr|qs) * delta(sigma_p,sigma_r) * delta(sigma_q,sigma_s) + ! ############################################################################# write(iunit, '(1X, A)') 'Forming antisymmetrised spinorbital ERIs...' allocate(int_store%asym_spinorb(sys%nbasis*2,sys%nbasis*2,sys%nbasis*2,sys%nbasis*2), source=0.0_dp, stat=ierr) call check_allocate('int_store%asym_spinorb', sys%nbasis**4*16, ierr) @@ -111,12 +126,18 @@ subroutine do_ccsd(sys, int_store) end do end associate + ! ############################################ + ! Initialise intermediate arrays and DIIS data + ! ############################################ call init_cc(sys, int_store, cc_amp, cc_int) allocate(st%t2_old, source=cc_amp%t_ijab) call init_diis_cc_t(sys, diis) write(iunit, '(1X, A)') 'Initialisation done, now entering iterative CC solver...' + ! ################### + ! Iterative CC solver + ! ################### associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab, asym=>int_store%asym_spinorb) do iter = 1, maxiter ! Update intermediate tensors @@ -124,6 +145,7 @@ subroutine do_ccsd(sys, int_store) call build_F(sys, cc_int, cc_amp, asym) call build_W(sys, cc_int, cc_amp, asym) + ! CC amplitude equations call update_amplitudes(sys, cc_amp, int_store, cc_int) call update_cc_energy(sys, st, int_store, cc_amp, conv) if (conv) then @@ -141,91 +163,22 @@ subroutine do_ccsd(sys, int_store) end do end associate + ! Nonlazy deallocations deallocate(st%t2_old) call deallocate_cc_int_t(cc_int) call deallocate_diis_cc_t(diis) end subroutine do_ccsd - subroutine update_diis_cc(diis, cc_amp) - use linalg, only: linsolve - use error_handling, only: error - - type(diis_cc_t), intent(inout) :: diis - type(cc_amp_t), intent(inout) :: cc_amp - - integer :: i, j, ierr - - diis%iter = diis%iter+1 - if (diis%iter > diis%n_errmat) diis%iter = diis%iter - diis%n_errmat - if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 - diis%t1(diis%iter,:,:) = 0.0_p - diis%t2(diis%iter,:,:,:,:) = 0.0_p - diis%t1(diis%iter,:,:) = cc_amp%t_ia - diis%t2(diis%iter,:,:,:,:) = cc_amp%t_ijab - - associate(n=>diis%n_active, nerr=>diis%n_errmat, it=>diis%iter, idx=>diis%idx) - if (n > 2) then - ! We need at least three CC iterations to have at least two error matrices - ! Construct index list (idx) - do i = 1, n-1 - idx(i,1) = mod(it+i+1, n)+1 - idx(i,2) = mod(it+i, n)+1 - end do - ! Construct the B matrix - if (n <= nerr) then - if (allocated(diis%B)) deallocate(diis%B, diis%c, diis%rhs) - allocate(diis%B(n+1,n+1), diis%c(n+1), diis%rhs(n+1), source=0.0_p) - end if - diis%B(n+1,:) = -1.0_p - diis%B(n+1,n+1) = 0.0_p - diis%rhs(n+1) = -1.0_p - diis%c = diis%rhs - do i = 1, n-1 - do j = 1, i - ! We compute the error matrices on the fly - ! [TODO] - shift iter index to the end to give better cache behaviour - diis%B(i,j) = sum((diis%t1(idx(i,1),:,:)-diis%t1(idx(i,2),:,:))*(diis%t1(idx(j,1),:,:)-diis%t1(idx(j,2),:,:))) & - + sum((diis%t2(idx(i,1),:,:,:,:)-diis%t2(idx(i,2),:,:,:,:))*(diis%t2(idx(j,1),:,:,:,:)-diis%t2(idx(j,2),:,:,:,:))) - end do - end do - call linsolve(diis%B, diis%c, ierr) - if (ierr /= 0) call error('ccsd::update_diis_cc', 'Linear solve failed!') - cc_amp%t_ia = 0.0_p - cc_amp%t_ijab = 0.0_p - do i = 1, n - cc_amp%t_ia = cc_amp%t_ia + diis%c(i) * diis%t1(i,:,:) - cc_amp%t_ijab = cc_amp%t_ijab + diis%c(i) * diis%t2(i,:,:,:,:) - end do - end if - end associate - end subroutine update_diis_cc - - subroutine init_diis_cc_t(sys, diis) - use error_handling, only: check_allocate - - type(system_t), intent(in) :: sys - type(diis_cc_t), intent(out) :: diis - - integer :: ierr - - allocate(diis%idx(diis%n_errmat,2), source=0) - - associate(n=>sys%nbasis, nocc=>sys%nocc) - allocate(diis%t1(diis%n_errmat,2*nocc,2*nocc+1:2*n), source=0.0_p, stat=ierr) - call check_allocate('diis%t1', diis%n_errmat*4*nocc*(n-nocc), ierr) - allocate(diis%t2(diis%n_errmat,2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_p, stat=ierr) - call check_allocate('diis%t1', diis%n_errmat*16*(nocc*(n-nocc))**2, ierr) - end associate - end subroutine init_diis_cc_t - - subroutine deallocate_diis_cc_t(diis) - type(diis_cc_t), intent(inout) :: diis - - deallocate(diis%t1, diis%t2, diis%B, diis%c, diis%rhs) - end subroutine deallocate_diis_cc_t - subroutine init_cc(sys, int_store, cc_amp, cc_int) + ! Initialise many CC related quantities. + ! In: + ! int_store: int_store_t object holding integrals. + ! In/out: + ! sys: system under study. + ! cc_amp: CC amplitudes + ! cc_int: CC intermediates being initialised + use integrals, only: int_store_t use error_handling, only: check_allocate @@ -255,6 +208,7 @@ subroutine init_cc(sys, int_store, cc_amp, cc_int) end do end do + ! This is only later useful in CCSD(T) but we can just do it here... allocate(sys%canon_levels_spinorb(2*n), source=0.0_dp) do i = 1, n sys%canon_levels_spinorb(2*i-1:2*i) = e(i) @@ -309,6 +263,10 @@ subroutine init_cc(sys, int_store, cc_amp, cc_int) end subroutine init_cc subroutine deallocate_cc_int_t(cc_int) + ! Nonlazy deallocation of the relatively large CC intermediate arrays. + ! In/out: + ! cc_int: cc_int_t object being deallocated. + type(cc_int_t), intent(inout) :: cc_int deallocate(cc_int%F_oo, cc_int%F_vv, cc_int%F_ov) @@ -318,155 +276,115 @@ subroutine deallocate_cc_int_t(cc_int) deallocate(cc_int%tmp_tia, cc_int%tmp_tijab) end subroutine + subroutine init_diis_cc_t(sys, diis) + ! Initialise CCSD DIIS quantities. Some are left unallocated as they need to be resized during the first few iterations. + ! In: + ! sys: system under study. + ! In/out: + ! diis: diis_cc_t object being initialised. - subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) - use integrals, only: int_store_t + use error_handling, only: check_allocate type(system_t), intent(in) :: sys - type(int_store_t), intent(in) :: int_store - type(cc_amp_t), intent(inout) :: cc_amp - type(cc_int_t), intent(inout) :: cc_int - - integer :: i, j, a, b, m, n, e, f - - associate(tmp_t1=>cc_int%tmp_tia,tmp_t2=>cc_int%tmp_tijab,t1=>cc_amp%t_ia,t2=>cc_amp%t_ijab,asym=>int_store%asym_spinorb, & - F_oo=>cc_int%F_oo,F_ov=>cc_int%F_ov,F_vv=>cc_int%F_vv,D_ia=>cc_int%D_ia,D_ijab=>cc_int%D_ijab,W_oooo=>cc_int%W_oooo, & - W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nbasis=>sys%nbasis,& - W_vvvv=>cc_int%W_vvvv) + type(diis_cc_t), intent(out) :: diis - ! Update T1 - !$omp parallel default(none) & - !$omp private(i, j, a, b, m, n, e, f) & - !$omp shared(sys, cc_amp, int_store, cc_int) + integer :: ierr - !$omp master - tmp_t1 = 0.0_dp - !$omp end master - !$omp do schedule(dynamic, 2) collapse(2) - do i = 1, 2*nocc - do a = 2*nocc+1, 2*nbasis - do m = 1, 2*nocc - tmp_t1(i,a) = tmp_t1(i,a) - t1(m,a)*F_oo(m,i) - do e = 2*nocc+1, 2*nbasis - tmp_t1(i,a) = tmp_t1(i,a) + t2(i,m,a,e)*F_ov(m,e) - do f = 2*nocc+1, 2*nbasis - tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(i,m,e,f)*asym(m,a,e,f) - end do - do n = 1, 2*nocc - tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(m,n,a,e)*asym(n,m,e,i) - end do - end do - end do - do e = 2*nocc+1, 2*nbasis - tmp_t1(i,a) = tmp_t1(i,a) + t1(i,e)*F_vv(a,e) - do n = 1, 2*nocc - tmp_t1(i,a) = tmp_t1(i,a) - t1(n,e)*asym(n,a,i,e) - end do - end do - end do - end do - !$omp end do + allocate(diis%idx(diis%n_errmat,2), source=0) - !$omp master - tmp_t1 = tmp_t1/D_ia - - ! Update T2 - tmp_t2 = 0.0_dp - !$omp end master + associate(n=>sys%nbasis, nocc=>sys%nocc) + allocate(diis%t1(diis%n_errmat,2*nocc,2*nocc+1:2*n), source=0.0_p, stat=ierr) + call check_allocate('diis%t1', diis%n_errmat*4*nocc*(n-nocc), ierr) + allocate(diis%t2(diis%n_errmat,2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_p, stat=ierr) + call check_allocate('diis%t1', diis%n_errmat*16*(nocc*(n-nocc))**2, ierr) + end associate + end subroutine init_diis_cc_t - !$omp do schedule(dynamic, 2) collapse(4) - do i = 1, 2*nocc - do j = 1, 2*nocc - do a = 2*nocc+1, 2*nbasis - do b = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = asym(i,j,a,b) - do e = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + t2(i,j,a,e)*F_vv(b,e) - t2(i,j,b,e)*F_vv(a,e) & - + tmp_t1(i,e)*asym(a,b,e,j) - tmp_t1(j,e)*asym(a,b,e,i) - do m = 1, 2*nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,j,a,e)*tmp_t1(m,b)-& - t2(i,j,b,e)*tmp_t1(m,a)) - end do - do f = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(i,j,e,f)*W_vvvv(a,b,e,f) - end do - end do - do m = 1, 2*nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(i,m,a,b)*F_oo(m,j) + t2(j,m,a,b)*F_oo(m,i) & - - tmp_t1(m,a)*asym(m,b,i,j) + tmp_t1(m,b)*asym(m,a,i,j) - do e = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*tmp_t1(j,e)-& - t2(j,m,a,b)*tmp_t1(i,e)) - end do - do n = 1, 2*nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(m,n,a,b)*W_oooo(m,n,i,j) - end do - end do + subroutine update_diis_cc(diis, cc_amp) + ! Update a DIIS iteration and form the new guess CC amplitudes (both singles and doubles). + ! In/out: + ! diis: the diis_cc_t object being updated + ! cc_amp: CC amplitudes being updated - do m = 1, 2*nocc - do e = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & - + t2(i,m,a,e)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*asym(m,b,e,j)& - - t2(j,m,a,e)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*asym(m,b,e,i)& - - t2(i,m,b,e)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*asym(m,a,e,j)& - + t2(j,m,b,e)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*asym(m,a,e,i) - end do - end do - end do - end do - end do - end do - !$omp end do - !$omp end parallel - t1 = tmp_t1 - t2 = tmp_t2/D_ijab - end associate + use linalg, only: linsolve + use error_handling, only: error - end subroutine update_amplitudes + type(diis_cc_t), intent(inout) :: diis + type(cc_amp_t), intent(inout) :: cc_amp - subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) - use system, only: state_t - use integrals, only: int_store_t + integer :: i, j, ierr - type(system_t), intent(in) :: sys - type(int_store_t), intent(in) :: int_store - type(cc_amp_t), intent(in) :: cc_amp - type(state_t), intent(inout) :: st - logical, intent(out) :: conv + diis%iter = diis%iter+1 + if (diis%iter > diis%n_errmat) diis%iter = diis%iter - diis%n_errmat + if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 + diis%t1(diis%iter,:,:) = 0.0_p + diis%t2(diis%iter,:,:,:,:) = 0.0_p + diis%t1(diis%iter,:,:) = cc_amp%t_ia + diis%t2(diis%iter,:,:,:,:) = cc_amp%t_ijab - integer :: i, j, a, b - real(p) :: ecc, rmst2 + associate(n=>diis%n_active, nerr=>diis%n_errmat, it=>diis%iter, idx=>diis%idx) + if (n > 2) then + ! We need at least three CC iterations to have at least two error matrices - conv = .false. - st%energy_old = st%energy - associate(nocc=>sys%nocc, nbasis=>sys%nbasis, asym=>int_store%asym_spinorb, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab) - !$omp parallel default(none) & - !$omp private(i,j,a,b) & - !$omp shared(sys,st,int_store,cc_amp,ecc,rmst2) - ecc = 0.0_p - rmst2 = 0.0_p - !$omp do schedule(dynamic, 2) collapse(4) reduction(+:ecc,rmst2) - do i = 1, 2*nocc - do j = 1, 2*nocc - do a = 2*nocc+1, 2*nbasis - do b = 2*nocc+1, 2*nbasis - ecc = ecc + 0.25*asym(i,j,a,b)*(t2(i,j,a,b)+2*t1(i,a)*t1(j,b)) - rmst2 = rmst2 + (t2(i,j,a,b)-st%t2_old(i,j,a,b))**2 - end do - end do + ! Construct index list (idx), see diis_cc_t documentation for motivation + ! Concrete example, say n_errmat=8, and we're at iteration 4 (overwriting the 4th T matrices), so the error matrices + ! should be: + ! e_1 = T4-T3 (== 4-3), e_2=3-2, e_3=2-1, e_4=1-8, e_5=8-7, e_6=7-6, e_7=6-5 + ! So out idx array should look like + ! 4 3 2 1 8 7 6 + ! 3 2 1 8 7 6 5 + ! (note that the code below gives something like this but with the columns swapped around but that's ok) + do i = 1, n-1 + idx(i,1) = mod(it+i+1, n)+1 + idx(i,2) = mod(it+i, n)+1 + end do + ! Construct the B matrix + if (n <= nerr) then + if (allocated(diis%B)) deallocate(diis%B, diis%c, diis%rhs) + allocate(diis%B(n+1,n+1), diis%c(n+1), diis%rhs(n+1), source=0.0_p) + end if + diis%B(n+1,:) = -1.0_p + diis%B(n+1,n+1) = 0.0_p + diis%rhs(n+1) = -1.0_p + diis%c = diis%rhs + do i = 1, n-1 + do j = 1, i + ! We compute the error matrices on the fly + ! [TODO] - shift iter index to the end to give better cache behaviour + diis%B(i,j) = sum((diis%t1(idx(i,1),:,:)-diis%t1(idx(i,2),:,:))*(diis%t1(idx(j,1),:,:)-diis%t1(idx(j,2),:,:))) & + + sum((diis%t2(idx(i,1),:,:,:,:)-diis%t2(idx(i,2),:,:,:,:))*(diis%t2(idx(j,1),:,:,:,:)-diis%t2(idx(j,2),:,:,:,:))) end do end do - !$omp end do - !$omp end parallel - st%energy = ecc - st%t2_old = t2 - if (sqrt(rmst2) < 1e-12 .and. abs(st%energy-st%energy_old) < 1e-12) conv = .true. - + call linsolve(diis%B, diis%c, ierr) + if (ierr /= 0) call error('ccsd::update_diis_cc', 'Linear solve failed!') + cc_amp%t_ia = 0.0_p + cc_amp%t_ijab = 0.0_p + do i = 1, n + cc_amp%t_ia = cc_amp%t_ia + diis%c(i) * diis%t1(i,:,:) + cc_amp%t_ijab = cc_amp%t_ijab + diis%c(i) * diis%t2(i,:,:,:,:) + end do + end if end associate + end subroutine update_diis_cc - end subroutine update_cc_energy + subroutine deallocate_diis_cc_t(diis) + ! Nonlazy deallocation of the diis_cc_t object as they take up significant memory + ! In/out: + ! diis: the diis_cc_t object being deallocated + + type(diis_cc_t), intent(inout) :: diis + + deallocate(diis%t1, diis%t2, diis%B, diis%c, diis%rhs) + end subroutine deallocate_diis_cc_t subroutine build_tau(sys, cc_amp, cc_int) + ! Build the effective singles and doubles operators. + ! In: + ! sys: system under study. + ! cc_amp: CC amplitudes. + ! In/out: + ! cc_int: CC intermediates with tau and tau_tilde updated + type(system_t), intent(in) :: sys type(cc_amp_t), intent(in) :: cc_amp type(cc_int_t), intent(inout) :: cc_int @@ -501,11 +419,20 @@ subroutine build_tau(sys, cc_amp, cc_int) end subroutine build_tau subroutine build_F(sys, cc_int, cc_amp, asym) - ! Eqs. 3-5, as we use HF reference all terms involving the fock matrix vanishes + ! Build the two-index F intermediates, + ! Eqs. 3-5, note as we use HF reference all terms involving the fock matrix vanishes. + ! In: + ! sys: System under study. + ! cc_amp: CC amplitudes + ! asym: the antisymmetrised two-electron integrals + ! In/out: + ! cc_int: CC intermediates with the F matrices updated. + type(system_t), intent(in) :: sys type(cc_amp_t), intent(in) :: cc_amp real(p), intent(in) :: asym(:,:,:,:) type(cc_int_t), intent(inout) :: cc_int + integer :: a, e, f, m, n, i associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& @@ -567,7 +494,17 @@ subroutine build_F(sys, cc_int, cc_amp, asym) end subroutine build_F subroutine build_W(sys, cc_int, cc_amp, asym) - ! Eqs. 6 and 8 + ! Build the four-index W intermediates, Eqs. 6 and 8. + ! Note that we use a factor of 0.5 in the innermost line of the W_oooo loop instead of 0.25 per main text of Stanton, + ! this is to make allowance for when W_vvvv cannot be stored due to memory limitation and has to be computed on the fly. + ! See appendix of the same paper. + ! In: + ! sys: System under study. + ! cc_amp: CC amplitudes + ! asym: the antisymmetrised two-electron integrals + ! In/out: + ! cc_int: CC intermediates with the F matrices updated. + type(system_t), intent(in) :: sys type(cc_amp_t), intent(in) :: cc_amp real(p), intent(in) :: asym(:,:,:,:) @@ -601,6 +538,7 @@ subroutine build_W(sys, cc_int, cc_amp, asym) end do !$omp end do + ! [TODO]: make a switch to on-the-fly W_vvvv computation, for when memory is limited !$omp do schedule(dynamic, 2) collapse(4) do a = 2*nocc+1, 2*nbasis do b = 2*nocc+1, 2*nbasis @@ -643,7 +581,179 @@ subroutine build_W(sys, cc_int, cc_amp, asym) end associate end subroutine build_W + subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) + ! Perform the CC amplitude equations + ! In: + ! sys: system under study. + ! int_store: integral information + ! In/out: + ! cc_amp: CC amplitudes being updated + ! cc_int: CC intermediates used in computing the updates + + use integrals, only: int_store_t + + type(system_t), intent(in) :: sys + type(int_store_t), intent(in) :: int_store + type(cc_amp_t), intent(inout) :: cc_amp + type(cc_int_t), intent(inout) :: cc_int + + integer :: i, j, a, b, m, n, e, f + + associate(tmp_t1=>cc_int%tmp_tia,tmp_t2=>cc_int%tmp_tijab,t1=>cc_amp%t_ia,t2=>cc_amp%t_ijab,asym=>int_store%asym_spinorb, & + F_oo=>cc_int%F_oo,F_ov=>cc_int%F_ov,F_vv=>cc_int%F_vv,D_ia=>cc_int%D_ia,D_ijab=>cc_int%D_ijab,W_oooo=>cc_int%W_oooo, & + W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nbasis=>sys%nbasis,& + W_vvvv=>cc_int%W_vvvv) + + ! Update T1 + !$omp parallel default(none) & + !$omp private(i, j, a, b, m, n, e, f) & + !$omp shared(sys, cc_amp, int_store, cc_int) + + !$omp master + tmp_t1 = 0.0_dp + !$omp end master + !$omp do schedule(dynamic, 2) collapse(2) + do i = 1, 2*nocc + do a = 2*nocc+1, 2*nbasis + do m = 1, 2*nocc + tmp_t1(i,a) = tmp_t1(i,a) - t1(m,a)*F_oo(m,i) + do e = 2*nocc+1, 2*nbasis + tmp_t1(i,a) = tmp_t1(i,a) + t2(i,m,a,e)*F_ov(m,e) + do f = 2*nocc+1, 2*nbasis + tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(i,m,e,f)*asym(m,a,e,f) + end do + do n = 1, 2*nocc + tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(m,n,a,e)*asym(n,m,e,i) + end do + end do + end do + do e = 2*nocc+1, 2*nbasis + tmp_t1(i,a) = tmp_t1(i,a) + t1(i,e)*F_vv(a,e) + do n = 1, 2*nocc + tmp_t1(i,a) = tmp_t1(i,a) - t1(n,e)*asym(n,a,i,e) + end do + end do + end do + end do + !$omp end do + + !$omp master + tmp_t1 = tmp_t1/D_ia + + ! Update T2 + tmp_t2 = 0.0_dp + !$omp end master + + !$omp do schedule(dynamic, 2) collapse(4) + do i = 1, 2*nocc + do j = 1, 2*nocc + do a = 2*nocc+1, 2*nbasis + do b = 2*nocc+1, 2*nbasis + tmp_t2(i,j,a,b) = asym(i,j,a,b) + do e = 2*nocc+1, 2*nbasis + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + t2(i,j,a,e)*F_vv(b,e) - t2(i,j,b,e)*F_vv(a,e) & + + tmp_t1(i,e)*asym(a,b,e,j) - tmp_t1(j,e)*asym(a,b,e,i) + do m = 1, 2*nocc + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,j,a,e)*tmp_t1(m,b)-& + t2(i,j,b,e)*tmp_t1(m,a)) + end do + do f = 2*nocc+1, 2*nbasis + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(i,j,e,f)*W_vvvv(a,b,e,f) + end do + end do + do m = 1, 2*nocc + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(i,m,a,b)*F_oo(m,j) + t2(j,m,a,b)*F_oo(m,i) & + - tmp_t1(m,a)*asym(m,b,i,j) + tmp_t1(m,b)*asym(m,a,i,j) + do e = 2*nocc+1, 2*nbasis + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*tmp_t1(j,e)-& + t2(j,m,a,b)*tmp_t1(i,e)) + end do + do n = 1, 2*nocc + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(m,n,a,b)*W_oooo(m,n,i,j) + end do + end do + + do m = 1, 2*nocc + do e = 2*nocc+1, 2*nbasis + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & + + t2(i,m,a,e)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*asym(m,b,e,j)& + - t2(j,m,a,e)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*asym(m,b,e,i)& + - t2(i,m,b,e)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*asym(m,a,e,j)& + + t2(j,m,b,e)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*asym(m,a,e,i) + end do + end do + end do + end do + end do + end do + !$omp end do + !$omp end parallel + t1 = tmp_t1 + t2 = tmp_t2/D_ijab + end associate + + end subroutine update_amplitudes + + subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) + ! Updates the CC energy and also checks for convergence + ! In: + ! sys: system under study. + ! int_store: integral information. + ! cc_amp: CC amplitudes. + ! In/out: + ! st: state_t object storing energies and RMS(T) info for convergence checking + ! Out: + ! conv: returns true if converged within tolerance + + use system, only: state_t + use integrals, only: int_store_t + + type(system_t), intent(in) :: sys + type(int_store_t), intent(in) :: int_store + type(cc_amp_t), intent(in) :: cc_amp + type(state_t), intent(inout) :: st + logical, intent(out) :: conv + + integer :: i, j, a, b + real(p) :: ecc, rmst2 + + conv = .false. + st%energy_old = st%energy + associate(nocc=>sys%nocc, nbasis=>sys%nbasis, asym=>int_store%asym_spinorb, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab) + !$omp parallel default(none) & + !$omp private(i,j,a,b) & + !$omp shared(sys,st,int_store,cc_amp,ecc,rmst2) + ecc = 0.0_p + rmst2 = 0.0_p + !$omp do schedule(dynamic, 2) collapse(4) reduction(+:ecc,rmst2) + do i = 1, 2*nocc + do j = 1, 2*nocc + do a = 2*nocc+1, 2*nbasis + do b = 2*nocc+1, 2*nbasis + ecc = ecc + 0.25*asym(i,j,a,b)*(t2(i,j,a,b)+2*t1(i,a)*t1(j,b)) + rmst2 = rmst2 + (t2(i,j,a,b)-st%t2_old(i,j,a,b))**2 + end do + end do + end do + end do + !$omp end do + !$omp end parallel + st%energy = ecc + st%t2_old = t2 + ! [TODO]: stop hard-coding tolerance, or at least unify it with HF + if (sqrt(rmst2) < 1e-12 .and. abs(st%energy-st%energy_old) < 1e-12) conv = .true. + + end associate + + end subroutine update_cc_energy + subroutine do_ccsd_t(sys, int_store) + ! Spinorbital formuation of CCSD(T) + ! In: + ! int_store: integral information. + ! In/out: + ! sys: holds converged amplitudes from CCSD + use integrals, only: int_store_t use error_handling, only: check_allocate @@ -712,5 +822,4 @@ subroutine do_ccsd_t(sys, int_store) print*, e_T end associate end subroutine do_ccsd_t - end module ccsd \ No newline at end of file From 225a3d32b505e1e256b4f1fee1d7cf8c1089cf2a Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 29 Dec 2021 11:57:25 +0000 Subject: [PATCH 38/71] Optimise loop order of mp2.f90, further documentation and clean-up --- src/ccsd.f90 | 40 +++++++++++++++------- src/hf.f90 | 9 ++--- src/integrals.f90 | 33 ++++++++++++------ src/mp2.f90 | 86 ++++++++++++++++++++++++++++------------------- src/system.f90 | 6 +++- 5 files changed, 111 insertions(+), 63 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 40e8384..dc8223d 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -27,7 +27,7 @@ module ccsd type diis_cc_t ! Contains information for use in the CCSD DIIS procedure ! Accelerating the convergence of the coupled-cluster approach: The use of the DIIS method - ! Gustavo E.ScuseriaTimothy J.LeeHenry F.SchaeferIII + ! Gustavo E. Scuseria, Timothy J. Lee, Henry F. Schaefer III ! (https://doi.org/10.1016/0009-2614(86)80461-4) ! These are identical as the HF-SCF ones, other than that we store and use the T matrices, @@ -330,7 +330,7 @@ subroutine update_diis_cc(diis, cc_amp) ! Concrete example, say n_errmat=8, and we're at iteration 4 (overwriting the 4th T matrices), so the error matrices ! should be: ! e_1 = T4-T3 (== 4-3), e_2=3-2, e_3=2-1, e_4=1-8, e_5=8-7, e_6=7-6, e_7=6-5 - ! So out idx array should look like + ! So our idx array should look like ! 4 3 2 1 8 7 6 ! 3 2 1 8 7 6 5 ! (note that the code below gives something like this but with the columns swapped around but that's ok) @@ -609,9 +609,11 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) !$omp private(i, j, a, b, m, n, e, f) & !$omp shared(sys, cc_amp, int_store, cc_int) - !$omp master + ! Implied barrier here, better than master which doesn't have implied barrier + ! tmp_t1 can be shared as each loop iteration will update a unique element of it. + !$omp single tmp_t1 = 0.0_dp - !$omp end master + !$omp end single !$omp do schedule(dynamic, 2) collapse(2) do i = 1, 2*nocc do a = 2*nocc+1, 2*nbasis @@ -637,12 +639,12 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do !$omp end do - !$omp master + !$omp single tmp_t1 = tmp_t1/D_ia ! Update T2 tmp_t2 = 0.0_dp - !$omp end master + !$omp end single !$omp do schedule(dynamic, 2) collapse(4) do i = 1, 2*nocc @@ -731,6 +733,7 @@ subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) do a = 2*nocc+1, 2*nbasis do b = 2*nocc+1, 2*nbasis ecc = ecc + 0.25*asym(i,j,a,b)*(t2(i,j,a,b)+2*t1(i,a)*t1(j,b)) + ! We only do the RMS on T2 amplitudes rmst2 = rmst2 + (t2(i,j,a,b)-st%t2_old(i,j,a,b))**2 end do end do @@ -741,7 +744,7 @@ subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) st%energy = ecc st%t2_old = t2 ! [TODO]: stop hard-coding tolerance, or at least unify it with HF - if (sqrt(rmst2) < 1e-12 .and. abs(st%energy-st%energy_old) < 1e-12) conv = .true. + if (sqrt(rmst2) < sys%ccsd_t_tol .and. abs(st%energy-st%energy_old) < sys%ccsd_e_tol) conv = .true. end associate @@ -753,7 +756,7 @@ subroutine do_ccsd_t(sys, int_store) ! int_store: integral information. ! In/out: ! sys: holds converged amplitudes from CCSD - + use integrals, only: int_store_t use error_handling, only: check_allocate @@ -763,6 +766,11 @@ subroutine do_ccsd_t(sys, int_store) integer :: i, j, k, a, b, c, f, m, ierr real(p), allocatable :: tmp_t3d(:,:,:), tmp_t3c(:,:,:), tmp_t3c_d(:,:,:) real(p) :: e_T + integer, parameter :: iunit = 6 + + write(iunit, '(1X, 10("-"))') + write(iunit, '(1X, A)') 'CCSD(T)' + write(iunit, '(1X, 10("-"))') associate(nbasis=>sys%nbasis, nocc=>sys%nocc, e=>sys%canon_levels_spinorb, t1=>sys%t1, t2=>sys%t2,& asym=>int_store%asym_spinorb) @@ -779,6 +787,11 @@ subroutine do_ccsd_t(sys, int_store) allocate(tmp_t3c_d(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) call check_allocate('tmp_t3c_d', 8*(nbasis-nocc)**3, ierr) + ! We use avoid the storage of full triples (six-dimensional array..) and instead use the strategy of + ! batched triples storage, denoted W^{ijk}(abc) in (https://doi.org/10.1016/0009-2614(91)87003-T). + ! We could of course only compute one element in a loop iteration but that will probably result in bad floating point + ! performance, here for each thread/loop iteration we use the Fortran intrinsic sum, + ! instead of all relying on OMP reduction, to hopefully give better floating point performance. !$omp do schedule(dynamic, 2) collapse(3) reduction(+:e_T) do i = 1, 2*nocc do j = 1, 2*nocc @@ -787,13 +800,15 @@ subroutine do_ccsd_t(sys, int_store) do a = 2*nocc+1, 2*nbasis do b = 2*nocc+1, 2*nbasis do c = 2*nocc+1, 2*nbasis - ! Disonnected T3: t_{ijk}^{abc}(d) = P(i/jk)P(a/bc)t_i^a* + ! Disonnected T3: D_{ijk}^{abc}*t_{ijk}^{abc}(d) = P(i/jk)P(a/bc)t_i^a* + ! Can be rewritten directly as no sums in the expression tmp_t3d(a,b,c) = t1(i,a)*asym(j,k,b,c) - t1(j,a)*asym(i,k,b,c) - t1(k,a)*asym(j,i,b,c) & - t1(i,b)*asym(j,k,a,c) + t1(j,b)*asym(i,k,a,c) + t1(k,b)*asym(j,i,a,c) & - t1(i,c)*asym(j,k,b,a) + t1(j,c)*asym(i,k,b,a) + t1(k,c)*asym(j,i,b,a) tmp_t3d(a,b,c) = tmp_t3d(a,b,c)/(e(i)+e(j)+e(k)-e(a)-e(b)-e(c)) - ! Conneccted T3: t_{ijk}^{abc}(c) = P(i/jk)P(a/bc)[\sum_f t_jk^af - \sum_m t_im^bc ] - + + ! Connected T3: D_{ijk}^{abc}*t_{ijk}^{abc}(c) = P(i/jk)P(a/bc)[\sum_f t_jk^af - \sum_m t_im^bc ] + ! Has to be zeroed as all terms are sums tmp_t3c(a,b,c) = 0.0_p do f = 2*nocc+1, 2*nbasis tmp_t3c(a,b,c) = tmp_t3c(a,b,c) & @@ -819,7 +834,8 @@ subroutine do_ccsd_t(sys, int_store) end do !$omp end do !$omp end parallel - print*, e_T + sys%e_ccsd_t = e_T + write(iunit, '(1X, A, 1X, F15.9)') 'CCSD(T) correlation energy (Hartree):', e_T end associate end subroutine do_ccsd_t end module ccsd \ No newline at end of file diff --git a/src/hf.f90 b/src/hf.f90 index 94f6bbc..cfeccd1 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -72,7 +72,7 @@ subroutine do_hartree_fock(sys, int_store) call build_density(fockmat%A, density, sys%nel/2) - call update_scf_energy(density, fockmat%ao, st, int_store, conv) + call update_scf_energy(sys, density, fockmat%ao, st, int_store, conv) if (conv) then write(iunit, '(1X, A)') 'Convergence reached within tolerance.' write(iunit, '(1X, A, 1X, F15.8)') 'Final SCF Energy (Hartree):', st%energy @@ -252,11 +252,12 @@ subroutine build_density(coeff, density, nocc) end subroutine build_density - subroutine update_scf_energy(density, fock, st, int_store, conv) + subroutine update_scf_energy(sys, density, fock, st, int_store, conv) - use system, only: state_t + use system, only: system_t, state_t use integrals, only: int_store_t + type(system_t), intent(in) :: sys real(p), intent(in) :: density(:,:) real(p), intent(in) :: fock(:,:) type(int_store_t), intent(in) :: int_store @@ -266,7 +267,7 @@ subroutine update_scf_energy(density, fock, st, int_store, conv) st%energy_old = st%energy st%energy = sum(density * (int_store%core_hamil + fock)) - if (sqrt(sum((density-st%density_old)**2)) < 1e-12 .and. abs(st%energy-st%energy_old) < 1e-12) conv = .true. + if (sqrt(sum((density-st%density_old)**2)) istart = [0, 1, 3, 6, ...] + ! 4 5 6 + ! 7 8 9 10 + ! So when we want to look up the array element (4,2) of the triangular array, stored in a flattened array, + ! the index of element at (4,2) in the flattened array is just istart(4) + 2 = 8 + + ! bignum should be bigger than n(n-1)/2 where n is the number of basis functions, so currently we can accommodate ~100 basis functions + integer, parameter :: bignum = 5000 + integer :: istart(bignum) type int_store_t real(p) :: e_nuc = 0.0_p @@ -125,7 +136,7 @@ subroutine read_integrals_in(sys, int_store) write(iunit, *) 'Reading two-body integrals...' open(newunit=ir, file=eri_f, status='old', form='formatted') - call init_ioff() + call init_istart() do read(ir, *, iostat=ios) ibasis, jbasis, abasis, bbasis, intgrl @@ -162,14 +173,14 @@ subroutine init_int_store(sys, int_store) end associate end subroutine init_int_store - subroutine init_ioff() + subroutine init_istart() integer :: i - ioff(1) = 1 + istart(1) = 0 do i = 2, bignum - ioff(i) = ioff(i-1) + i-1 + istart(i) = istart(i-1) + i-1 end do - end subroutine + end subroutine init_istart elemental function eri_ind(i, j) result(ind) ! This function can be a general version for i,j,a,b, but @@ -180,9 +191,9 @@ elemental function eri_ind(i, j) result(ind) integer :: ind if (i >= j) then - ind = ioff(i) + j-1 + ind = istart(i) + j else - ind = ioff(j) + i-1 + ind = istart(j) + i end if end function eri_ind diff --git a/src/mp2.f90 b/src/mp2.f90 index 0b71fd1..ad800fd 100644 --- a/src/mp2.f90 +++ b/src/mp2.f90 @@ -86,8 +86,7 @@ subroutine do_mp2(sys, int_store) type(system_t), intent(inout) :: sys type(int_store_t), intent(inout) :: int_store - real(dp), allocatable :: tmp_a(:,:,:,:) - real(dp), allocatable :: tmp_b(:,:,:,:) ! mixed integrals like (ij|rs) + real(dp), allocatable :: tmp_a(:,:,:,:), tmp_b(:,:,:,:) integer :: tmpdim, n, nocc integer :: i, j, k, l, p, q, r, s, a, b integer :: kl, ij, pq, rs, pqrs, s_up @@ -108,18 +107,42 @@ subroutine do_mp2(sys, int_store) allocate(int_store%eri_mo, mold=int_store%eri) - !$omp parallel default(none) & !$omp private(kl, ij, pq, rs, pqrs, s_up, ia, ja, jb, ib) & !$omp shared(sys, int_store, tmp_a, tmp_b, nocc, n) associate(C=>sys%canon_coeff, eri_mo=>int_store%eri_mo, eri=>int_store%eri) !$omp do schedule(dynamic, 2) collapse(2) + + ! Naively (see above) we can perform the transformation of (ij|kl)->(pq|rs) in an O(N^8) loop: + ! do ijklpqrs + ! (pq|rs) = C_pi C_qj C_rk C_sl (ij|kl) + ! end do + ! + ! But we can also, with the aid of two 4-dimensional temp matrices, perform 4 O(N^5) loops: + ! do ijklp + ! (pj|kl) (tmp_a) += (ij|kl) * C_pi + ! end do + ! do pjklq + ! (pq|kl) (tmp_b) += (pj|kl) (tmp_a) * C_qj + ! end do + ! do pqklr + ! (pq|rl) (tmp_a) += (pq|kl) (tmp_b) * C_rk + ! end do + ! do pqrls + ! (pq|rs) (tmp_b) += (pq|rl) (tmp_a) * C_sl + ! end do + ! + ! One last loop to store in one dimensional array with perm. symmetry... + + ! Notice the order of the loops are optimised for Fortran coloumn major array storage: + ! the first index varies the fastest etc. + ! (ij|kl) -> (pj|kl) - do k = 1, n - do l = 1, n + do l = 1, n + do k = 1, n kl = eri_ind(k,l) - do j = 1, n - do i = 1, n + do i = 1, n + do j = 1, n ij = eri_ind(i,j) do p = 1, n tmp_a(p,j,k,l) = tmp_a(p,j,k,l) + eri(eri_ind(ij,kl))*C(p,i) @@ -132,12 +155,11 @@ subroutine do_mp2(sys, int_store) !$omp do schedule(dynamic, 2) collapse(2) ! (pj|kl) -> (pq|kl) - do k = 1, n - do l = 1, n - kl = eri_ind(k,l) - do p = 1, n - do j = 1, n - do q = 1, n + do l = 1, n + do k = 1, n + do j = 1, n + do q = 1, n + do p = 1, n tmp_b(p,q,k,l) = tmp_b(p,q,k,l) + tmp_a(p,j,k,l)*C(q,j) end do end do @@ -147,18 +169,16 @@ subroutine do_mp2(sys, int_store) !$omp end do ! (pq|kl) -> (pq|rl) - !$omp master + !$omp single tmp_a(:,:,:,:) = 0.0_dp - !$omp end master + !$omp end single !$omp do schedule(dynamic, 2) collapse(2) - do p = 1, n - do q = 1, n - pq = eri_ind(p,q) + do l = 1, n + do r = 1, n do k = 1, n - do l = 1, n - kl = eri_ind(k,l) - do r = 1, n + do q = 1, n + do p = 1, n tmp_a(p,q,r,l) = tmp_a(p,q,r,l) + tmp_b(p,q,k,l)*C(r,k) end do end do @@ -168,17 +188,15 @@ subroutine do_mp2(sys, int_store) !$omp end do ! (pq|rl) -> (pq|rs) - !$omp master + !$omp single tmp_b(:,:,:,:) = 0.0_dp - !$omp end master + !$omp end single !$omp do schedule(dynamic, 2) collapse(2) - do p = 1, n - do q = 1, n - pq = eri_ind(p,q) - do r = 1, n - do l = 1, n - do s = 1, n - rs = eri_ind(r,s) + do s = 1, n + do r = 1, n + do l = 1, n + do q = 1, n + do p = 1, n tmp_b(p,q,r,s) = tmp_b(p,q,r,s) + tmp_a(p,q,r,l)*C(s,l) end do end do @@ -187,7 +205,7 @@ subroutine do_mp2(sys, int_store) end do !$omp end do - !$omp master + !$omp single pq = 0 pqrs = 0 do p = 1, n @@ -203,12 +221,12 @@ subroutine do_mp2(sys, int_store) end if do s = 1, s_up pqrs = pqrs + 1 - eri_mo(pqrs) = tmp_b(p,q,r,s) + eri_mo(pqrs) = tmp_b(s,r,q,p) end do end do end do end do - !$omp end master + !$omp end single end associate !$omp end parallel @@ -238,7 +256,5 @@ subroutine do_mp2(sys, int_store) write(iunit, '(1X, A, 1X, F15.8)') 'MP2 correlation energy (Hartree):', sys%e_mp2 end subroutine do_mp2 - - end module mp2 \ No newline at end of file diff --git a/src/system.f90 b/src/system.f90 index 593fad2..f57d3d7 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -28,7 +28,11 @@ module system real(p), allocatable :: t1(:,:) real(p), allocatable :: t2(:,:,:,:) - + ! Tolerances + real(p) :: scf_e_tol = 1e-6 + real(p) :: scf_d_tol = 1e-6 + real(p) :: ccsd_e_tol = 1e-6 + real(p) :: ccsd_t_tol = 1e-6 end type system_t From 0a9e11f31d6c3cd6918dba96de3793b1dfcfccbb Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 29 Dec 2021 16:08:35 +0000 Subject: [PATCH 39/71] First attempt at cache optimisation, mp2 quite successful but ccsd/(t) less so --- src/ccsd.f90 | 49 ++++++++++++++++++++++++------------------------- src/mp2.f90 | 1 + 2 files changed, 25 insertions(+), 25 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index dc8223d..275f171 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -400,13 +400,12 @@ subroutine build_tau(sys, cc_amp, cc_int) !$omp private(i,j,a,b,ia,ja,x) & !$omp shared(sys, cc_amp, cc_int) & !$omp schedule(dynamic, 2) collapse(2) - do i = 1, 2*nocc + do b = 2*nocc+1, 2*n do a = 2*nocc+1, 2*n - ia = t_ia(i,a) do j = 1, 2*nocc ja = t_ia(j,a) - do b = 2*nocc+1, 2*n - x = ia*t_ia(j,b) - t_ia(i,b)*ja + do i = 1, 2*nocc + x = t_ia(i,a)*t_ia(j,b) - t_ia(i,b)*ja tau_tilde(i,j,a,b) = t_ijab(i,j,a,b) + 0.5*x tau(i,j,a,b) = tau_tilde(i,j,a,b) + 0.5*x end do @@ -527,9 +526,9 @@ subroutine build_W(sys, cc_int, cc_amp, asym) do j = 1, 2*nocc W_oooo(m,n,i,j) = asym(m,n,i,j) do e = 2*nocc+1, 2*nbasis - W_oooo(m,n,i,j) = W_oooo(m,n,i,j) + t_ia(j,e)*asym(m,n,i,e) - t_ia(i,e)*asym(m,n,j,e) + W_oooo(m,n,i,j) = W_oooo(m,n,i,j) + t_ia(j,e)*asym(m,n,i,e) + t_ia(i,e)*asym(e,j,m,n) do f = 2*nocc+1, 2*nbasis - W_oooo(m,n,i,j) = W_oooo(m,n,i,j) + 0.5*t_ijab(i,j,e,f)*asym(m,n,e,f) + W_oooo(m,n,i,j) = W_oooo(m,n,i,j) - 0.5*t_ijab(i,j,e,f)*asym(f,e,m,n) end do end do end do @@ -540,13 +539,13 @@ subroutine build_W(sys, cc_int, cc_amp, asym) ! [TODO]: make a switch to on-the-fly W_vvvv computation, for when memory is limited !$omp do schedule(dynamic, 2) collapse(4) - do a = 2*nocc+1, 2*nbasis - do b = 2*nocc+1, 2*nbasis - do e = 2*nocc+1, 2*nbasis - do f = 2*nocc+1, 2*nbasis + do f = 2*nocc+1, 2*nbasis + do e = 2*nocc+1, 2*nbasis + do b = 2*nocc+1, 2*nbasis + do a = 2*nocc+1, 2*nbasis W_vvvv(a,b,e,f) = asym(a,b,e,f) do n = 1, 2*nocc - W_vvvv(a,b,e,f) = W_vvvv(a,b,e,f) - t_ia(n,b)*asym(a,n,e,f) + t_ia(n,a)*asym(b,n,e,f) + W_vvvv(a,b,e,f) = W_vvvv(a,b,e,f) + t_ia(n,b)*asym(n,a,e,f) - t_ia(n,a)*asym(n,b,e,f) end do end do end do @@ -561,14 +560,14 @@ subroutine build_W(sys, cc_int, cc_amp, asym) do j = 1, 2*nocc W_ovvo(m,b,e,j) = asym(m,b,e,j) do f = 2*nocc+1, 2*nbasis - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) + t_ia(j,f)*asym(m,b,e,f) + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - t_ia(j,f)*asym(f,e,m,b) end do do n = 1, 2*nocc x = t_ia(n,b) W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - x*asym(m,n,e,j) do f = 2*nocc+1, 2*nbasis - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t_ijab(j,n,f,b) + x*t_ia(j,f)) * asym(m,n,e,f) + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t_ijab(j,n,f,b) - x*t_ia(j,f)) * asym(f,e,m,n) end do end do end do @@ -622,7 +621,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) do e = 2*nocc+1, 2*nbasis tmp_t1(i,a) = tmp_t1(i,a) + t2(i,m,a,e)*F_ov(m,e) do f = 2*nocc+1, 2*nbasis - tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(i,m,e,f)*asym(m,a,e,f) + tmp_t1(i,a) = tmp_t1(i,a) + 0.5*t2(i,m,e,f)*asym(f,e,m,a) end do do n = 1, 2*nocc tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(m,n,a,e)*asym(n,m,e,i) @@ -678,10 +677,10 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) do m = 1, 2*nocc do e = 2*nocc+1, 2*nbasis tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & - + t2(i,m,a,e)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*asym(m,b,e,j)& - - t2(j,m,a,e)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*asym(m,b,e,i)& - - t2(i,m,b,e)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*asym(m,a,e,j)& - + t2(j,m,b,e)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*asym(m,a,e,i) + + t2(i,m,a,e)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*asym(e,j,m,b)& + - t2(j,m,a,e)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*asym(e,i,m,b)& + - t2(i,m,b,e)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*asym(e,j,m,a)& + + t2(j,m,b,e)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*asym(e,i,m,a) end do end do end do @@ -728,10 +727,10 @@ subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) ecc = 0.0_p rmst2 = 0.0_p !$omp do schedule(dynamic, 2) collapse(4) reduction(+:ecc,rmst2) - do i = 1, 2*nocc - do j = 1, 2*nocc - do a = 2*nocc+1, 2*nbasis - do b = 2*nocc+1, 2*nbasis + do b = 2*nocc+1, 2*nbasis + do a = 2*nocc+1, 2*nbasis + do j = 1, 2*nocc + do i = 1, 2*nocc ecc = ecc + 0.25*asym(i,j,a,b)*(t2(i,j,a,b)+2*t1(i,a)*t1(j,b)) ! We only do the RMS on T2 amplitudes rmst2 = rmst2 + (t2(i,j,a,b)-st%t2_old(i,j,a,b))**2 @@ -802,9 +801,9 @@ subroutine do_ccsd_t(sys, int_store) do c = 2*nocc+1, 2*nbasis ! Disonnected T3: D_{ijk}^{abc}*t_{ijk}^{abc}(d) = P(i/jk)P(a/bc)t_i^a* ! Can be rewritten directly as no sums in the expression - tmp_t3d(a,b,c) = t1(i,a)*asym(j,k,b,c) - t1(j,a)*asym(i,k,b,c) - t1(k,a)*asym(j,i,b,c) & - - t1(i,b)*asym(j,k,a,c) + t1(j,b)*asym(i,k,a,c) + t1(k,b)*asym(j,i,a,c) & - - t1(i,c)*asym(j,k,b,a) + t1(j,c)*asym(i,k,b,a) + t1(k,c)*asym(j,i,b,a) + tmp_t3d(a,b,c) = - t1(i,a)*asym(c,b,j,k) + t1(j,a)*asym(c,b,i,k) + t1(k,a)*asym(c,b,j,i) & + + t1(i,b)*asym(c,a,j,k) - t1(j,b)*asym(c,a,i,k) - t1(k,b)*asym(c,a,j,i) & + - t1(i,c)*asym(j,k,b,a) + t1(j,c)*asym(i,k,b,a) + t1(k,c)*asym(j,i,b,a) tmp_t3d(a,b,c) = tmp_t3d(a,b,c)/(e(i)+e(j)+e(k)-e(a)-e(b)-e(c)) ! Connected T3: D_{ijk}^{abc}*t_{ijk}^{abc}(c) = P(i/jk)P(a/bc)[\sum_f t_jk^af - \sum_m t_im^bc ] diff --git a/src/mp2.f90 b/src/mp2.f90 index ad800fd..350ce10 100644 --- a/src/mp2.f90 +++ b/src/mp2.f90 @@ -221,6 +221,7 @@ subroutine do_mp2(sys, int_store) end if do s = 1, s_up pqrs = pqrs + 1 + ! use full permutational symmetry to optimise cache behaviour eri_mo(pqrs) = tmp_b(s,r,q,p) end do end do From 2f20d8169a3f772d50921a063a96a9f528db6d6c Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 29 Dec 2021 17:26:43 +0000 Subject: [PATCH 40/71] Update README.md --- README.md | 3 ++- 1 file changed, 2 insertions(+), 1 deletion(-) diff --git a/README.md b/README.md index fcffcf4..8d15e6f 100644 --- a/README.md +++ b/README.md @@ -14,7 +14,8 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [X] DIIS acceleration for Hartree-Fock SCF - [X] CCSD(T) without symmetry - [X] DIIS acceleration for CCSD iterations -- [ ] Loop optimisations (fusing triangular loops, cache optimisations) +- [X] Loop optimisations - cache +- [ ] Loop optimisations - using permutational symmetry - [ ] Adapting Hartree-Fock with symmetry - [ ] Ditto for MP2 - [ ] Ditto for CCSD From a93933dca3374e9410f62da6c8f43cdb21a8dfc5 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 29 Dec 2021 17:31:11 +0000 Subject: [PATCH 41/71] Update README.md --- README.md | 1 + 1 file changed, 1 insertion(+) diff --git a/README.md b/README.md index 8d15e6f..8c68fb0 100644 --- a/README.md +++ b/README.md @@ -22,3 +22,4 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [ ] Ditto for CCSD(T) - [ ] MPI parallelisation - [ ] GPU adaptation for MP2 and CCSD/(T) +- [ ] User input file: level of theory, tolerances From d4b474b03d175d1d006c0f8840a0e1d68689300f Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sat, 1 Jan 2022 21:07:48 +0000 Subject: [PATCH 42/71] Fix wrong CCSD energy, add per-iteration time --- src/ccsd.f90 | 77 ++++++++++++++++++++++++++++++++++++++++------------ 1 file changed, 60 insertions(+), 17 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 275f171..6939877 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -57,7 +57,7 @@ subroutine do_ccsd(sys, int_store) ! [TODO]: closed-shell (spatial) formulation of Hirata, S.; Podeszwa, R.; Tobita, M.; Bartlett, R. J. J. Chem. Phys. 2004, 120 (6), 2581 (https://doi.org/10.1063/1.1637577) use integrals, only: int_store_t, eri_ind - use error_handling, only: check_allocate + use error_handling, only: error, check_allocate use system, only: state_t type(system_t), intent(inout) :: sys @@ -65,6 +65,8 @@ subroutine do_ccsd(sys, int_store) integer :: i, j, a, b, p, q, r, s integer :: pr, qr, pa, pb, qa, qb, ra, rb, sa, sb real(dp) :: prqs, psqr + real(dp) :: err + integer(kind=8) :: c_max, c_rate, t0, t1 type(state_t) :: st type(diis_cc_t) :: diis @@ -86,11 +88,10 @@ subroutine do_ccsd(sys, int_store) ! where = (pr|qs) * delta(sigma_p,sigma_r) * delta(sigma_q,sigma_s) ! ############################################################################# write(iunit, '(1X, A)') 'Forming antisymmetrised spinorbital ERIs...' + call system_clock(count=t0, count_rate=c_rate, count_max=c_max) allocate(int_store%asym_spinorb(sys%nbasis*2,sys%nbasis*2,sys%nbasis*2,sys%nbasis*2), source=0.0_dp, stat=ierr) call check_allocate('int_store%asym_spinorb', sys%nbasis**4*16, ierr) - call init_diis_cc_t(sys, diis) - associate(n=>sys%nbasis, asym=>int_store%asym_spinorb, eri=>int_store%eri_mo) ! [TODO]: this isn't necessary but easier for debugging, change to spin lookup arrays or something similar do p = 1, n @@ -125,14 +126,52 @@ subroutine do_ccsd(sys, int_store) end do end do end associate + call system_clock(t1) + if (t1sys%nbasis, asym=>int_store%asym_spinorb) + do p = 1, 2*nbasis + do q = 1, p + do r = 1, p + do s = 1, min(r,p) + err = err + abs(asym(p,q,r,s) + asym(p,q,s,r)) + abs(asym(p,q,r,s) - asym(r,s,p,q)) & + + abs(asym(p,q,r,s) + asym(s,r,p,q)) + abs(asym(p,q,r,s) - asym(s,r,q,p)) + end do + end do + end do + end do + end associate + + if (err > depsilon) then + write(iunit, '(1X, A, 1X, E15.6)') 'Permutational symmetry error:', err + call error('ccsd::do_ccsd', 'Permutational symmetry of antisymmetrised integrals does not hold') + end if + + call system_clock(t1) + if (t1 Date: Tue, 4 Jan 2022 11:57:09 +0000 Subject: [PATCH 43/71] Add utility to generate integrals with permutational sym --- utils/psi4_integrals.py | 59 +++++++++++++++++++++++++++++++++++++++++ 1 file changed, 59 insertions(+) create mode 100644 utils/psi4_integrals.py diff --git a/utils/psi4_integrals.py b/utils/psi4_integrals.py new file mode 100644 index 0000000..297e72a --- /dev/null +++ b/utils/psi4_integrals.py @@ -0,0 +1,59 @@ +#!/usr/bin/env python +# coding: utf-8 + +import psi4 +import numpy as np + +bl = 2.0787 # Angstroms +ang = 104.45 # Degrees +psi4.set_memory('2000 MB') +mol = psi4.geometry(f""" + O 0 -0.143225816552 0 + H 1.638036840407 1.136548822547 0 + H -1.638036840407 1.136548822547 0 + units = bohr + """) +psi4.set_options({'basis':'sto-3g'}) +wfn = psi4.core.Wavefunction(mol, psi4.core.BasisSet.build(mol)) +mints = psi4.core.MintsHelper(wfn.basisset()) +S = mints.ao_overlap().nph +T = mints.ao_kinetic().nph +V = mints.ao_potential().nph +eri = mints.ao_eri().nph +S_so = mints.so_overlap().nph +T_so = mints.so_kinetic().nph +V_so = mints.so_potential().nph + +def lowtri_array(start, interval): + idx = [] + for i in range(interval+1): + for j in range(i): + idx.append([i+start, j+1+start]) + return np.array(idx) + +def ints2perm(ints): + # Input is a tuple of arrays + nrows = 0 + norb = 0 + for i in range(len(ints)): + nrows += int(ints[i].shape[0]*(ints[i].shape[0]+1)/2) + perm = [np.array([]),np.array([]),np.array([])] + for i in range(len(ints)): + if len(ints[i]) != 0: + idx = lowtri_array(norb, ints[i].shape[0]) + norb += ints[i].shape[0] + perm[0] = np.append(perm[0],idx[:,0]) + perm[1] = np.append(perm[1],idx[:,1]) + perm[2] = np.append(perm[2],lower_triangular(ints[i])) + return np.stack((perm[:])).T + +def lower_triangular(mat): + flat = [] + for i in range(mat.shape[0]): + for j in range(i+1): + flat.append(mat[i,j]) + return flat + +s_perm = ints2perm(S_so) + +np.savetxt('s.dat', s_perm, ['%1d','%1d','%17.15f'], delimiter='\t') \ No newline at end of file From 0c90bee92af4e80d8ff35059de33feab1195bc35 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 17 Jan 2022 20:57:19 +0000 Subject: [PATCH 44/71] Add system read_in functionality --- src/ccsd.f90 | 76 +++++++++++++++++++++++++------------------------- src/hf.f90 | 64 ++++++++++++++++++++---------------------- src/main.F90 | 5 ++-- src/system.f90 | 38 ++++++++++++++++++++++++- 4 files changed, 108 insertions(+), 75 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 6939877..684679c 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -442,7 +442,7 @@ subroutine build_tau(sys, cc_amp, cc_int) !$omp parallel do default(none) & !$omp private(i,j,a,b,ia,ja,x) & !$omp shared(sys, cc_amp, cc_int) & - !$omp schedule(dynamic, 2) collapse(2) + !$omp schedule(runtime) collapse(2) do b = 2*nocc+1, 2*n do a = 2*nocc+1, 2*n do j = 1, 2*nocc @@ -488,14 +488,14 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp private(a, e, f, m, n, i) & !$omp shared(sys, cc_int, cc_amp, asym) - !$omp do schedule(dynamic, 2) collapse(2) + !$omp do schedule(runtime) collapse(2) do a = 2*nocc+1, 2*nbasis do e = 2*nocc+1, 2*nbasis do m = 1, 2*nocc do f = 2*nocc+1, 2*nbasis F_vv(a,e) = F_vv(a,e) + t_ia(m,f) * asym(f,e,m,a) do n = 1, 2*nocc - F_vv(a,e) = F_vv(a,e) + 0.5*tau_tilde(m,n,a,f)*asym(n,m,e,f) + F_vv(a,e) = F_vv(a,e) + 0.5*tau_tilde(n,m,f,a)*asym(n,m,e,f) end do end do end do @@ -504,14 +504,14 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp end do ! F_mi = \sum_{en} t_n^e + 0.5 \sum_{nef} \tau~_{in}^{ef} - !$omp do schedule(dynamic, 2) collapse(2) + !$omp do schedule(runtime) collapse(2) do m = 1, 2*nocc do i = 1, 2*nocc do e = 2*nocc+1, 2*nbasis do n = 1, 2*nocc F_oo(m,i) = F_oo(m,i) - t_ia(n,e)*asym(n,m,i,e) do f = 2*nocc+1, 2*nbasis - F_oo(m,i) = F_oo(m,i) - 0.5*tau_tilde(i,n,e,f)*asym(f,e,m,n) + F_oo(m,i) = F_oo(m,i) - 0.5*tau_tilde(n,i,f,e)*asym(f,e,m,n) end do end do end do @@ -520,7 +520,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp end do ! F_me = \sum_{nf} t_n^f * - !$omp do schedule(dynamic, 2) collapse(2) + !$omp do schedule(runtime) collapse(2) do m = 1, 2*nocc do e = 2*nocc+1, 2*nbasis do n = 1, 2*nocc @@ -562,7 +562,7 @@ subroutine build_W(sys, cc_int, cc_amp, asym) !$omp private(m, n, i, j, e, f, b, x, a) & !$omp shared(sys, cc_int, cc_amp, asym) - !$omp do schedule(dynamic, 2) collapse(4) + !$omp do schedule(runtime) collapse(4) do m = 1, 2*nocc do n = 1, 2*nocc do i = 1, 2*nocc @@ -571,7 +571,7 @@ subroutine build_W(sys, cc_int, cc_amp, asym) do e = 2*nocc+1, 2*nbasis W_oooo(m,n,i,j) = W_oooo(m,n,i,j) + t_ia(j,e)*asym(e,i,n,m) - t_ia(i,e)*asym(e,j,n,m) do f = 2*nocc+1, 2*nbasis - W_oooo(m,n,i,j) = W_oooo(m,n,i,j) - 0.5*t_ijab(i,j,e,f)*asym(f,e,m,n) + W_oooo(m,n,i,j) = W_oooo(m,n,i,j) - 0.5*t_ijab(j,i,f,e)*asym(f,e,m,n) end do end do end do @@ -581,7 +581,7 @@ subroutine build_W(sys, cc_int, cc_amp, asym) !$omp end do ! [TODO]: make a switch to on-the-fly W_vvvv computation, for when memory is limited - !$omp do schedule(dynamic, 2) collapse(4) + !$omp do schedule(runtime) collapse(4) do f = 2*nocc+1, 2*nbasis do e = 2*nocc+1, 2*nbasis do b = 2*nocc+1, 2*nbasis @@ -596,7 +596,7 @@ subroutine build_W(sys, cc_int, cc_amp, asym) end do !$omp end do - !$omp do schedule(dynamic, 2) collapse(4) + !$omp do schedule(runtime) collapse(4) do j = 1, 2*nocc do e = 2*nocc+1, 2*nbasis do b = 2*nocc+1, 2*nbasis @@ -656,18 +656,18 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) !$omp single tmp_t1 = 0.0_dp !$omp end single - !$omp do schedule(dynamic, 2) collapse(2) - do i = 1, 2*nocc - do a = 2*nocc+1, 2*nbasis + !$omp do schedule(runtime) collapse(2) + do a = 2*nocc+1, 2*nbasis + do i = 1, 2*nocc do m = 1, 2*nocc tmp_t1(i,a) = tmp_t1(i,a) - t1(m,a)*F_oo(m,i) do e = 2*nocc+1, 2*nbasis - tmp_t1(i,a) = tmp_t1(i,a) + t2(i,m,a,e)*F_ov(m,e) + tmp_t1(i,a) = tmp_t1(i,a) + t2(m,i,e,a)*F_ov(m,e) do f = 2*nocc+1, 2*nbasis - tmp_t1(i,a) = tmp_t1(i,a) + 0.5*t2(i,m,e,f)*asym(f,e,m,a) + tmp_t1(i,a) = tmp_t1(i,a) + 0.5*t2(m,i,f,e)*asym(f,e,m,a) end do do n = 1, 2*nocc - tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(m,n,a,e)*asym(n,m,e,i) + tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(n,m,e,a)*asym(n,m,e,i) end do end do end do @@ -688,42 +688,42 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) tmp_t2 = 0.0_dp !$omp end single - !$omp do schedule(dynamic, 2) collapse(4) - do i = 1, 2*nocc - do j = 1, 2*nocc - do a = 2*nocc+1, 2*nbasis - do b = 2*nocc+1, 2*nbasis + !$omp do schedule(runtime) collapse(4) + do b = 2*nocc+1, 2*nbasis + do a = 2*nocc+1, 2*nbasis + do j = 1, 2*nocc + do i = 1, 2*nocc tmp_t2(i,j,a,b) = asym(i,j,a,b) do e = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + t2(i,j,a,e)*F_vv(b,e) - t2(i,j,b,e)*F_vv(a,e) & - + tmp_t1(i,e)*asym(a,b,e,j) - tmp_t1(j,e)*asym(a,b,e,i) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + t2(j,i,e,a)*F_vv(b,e) - t2(j,i,e,b)*F_vv(a,e) & + + tmp_t1(i,e)*asym(e,j,a,b) - tmp_t1(j,e)*asym(e,i,a,b) do m = 1, 2*nocc tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,j,a,e)*tmp_t1(m,b)-& t2(i,j,b,e)*tmp_t1(m,a)) end do do f = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(i,j,e,f)*W_vvvv(a,b,e,f) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(j,i,f,e)*W_vvvv(a,b,e,f) end do end do do m = 1, 2*nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(i,m,a,b)*F_oo(m,j) + t2(j,m,a,b)*F_oo(m,i) & + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(m,i,b,a)*F_oo(m,j) + t2(m,j,b,a)*F_oo(m,i) & - tmp_t1(m,a)*asym(m,b,i,j) + tmp_t1(m,b)*asym(m,a,i,j) do e = 2*nocc+1, 2*nbasis tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*tmp_t1(j,e)-& t2(j,m,a,b)*tmp_t1(i,e)) end do do n = 1, 2*nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(m,n,a,b)*W_oooo(m,n,i,j) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(n,m,b,a)*W_oooo(m,n,i,j) end do end do do m = 1, 2*nocc do e = 2*nocc+1, 2*nbasis tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & - + t2(i,m,a,e)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*asym(e,j,m,b)& - - t2(j,m,a,e)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*asym(e,i,m,b)& - - t2(i,m,b,e)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*asym(e,j,m,a)& - + t2(j,m,b,e)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*asym(e,i,m,a) + + t2(m,i,e,a)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*asym(e,j,m,b)& + - t2(m,j,e,a)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*asym(e,i,m,b)& + - t2(m,i,e,b)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*asym(e,j,m,a)& + + t2(m,j,e,b)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*asym(e,i,m,a) end do end do end do @@ -769,7 +769,7 @@ subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) !$omp shared(sys,st,int_store,cc_amp,ecc,rmst2) ecc = 0.0_p rmst2 = 0.0_p - !$omp do schedule(dynamic, 2) collapse(4) reduction(+:ecc,rmst2) + !$omp do schedule(runtime) collapse(4) reduction(+:ecc,rmst2) do b = 2*nocc+1, 2*nbasis do a = 2*nocc+1, 2*nbasis do j = 1, 2*nocc @@ -834,7 +834,7 @@ subroutine do_ccsd_t(sys, int_store) ! We could of course only compute one element in a loop iteration but that will probably result in bad floating point ! performance, here for each thread/loop iteration we use the Fortran intrinsic sum, ! instead of all relying on OMP reduction, to hopefully give better floating point performance. - !$omp do schedule(dynamic, 2) collapse(3) reduction(+:e_T) + !$omp do schedule(runtime) collapse(3) reduction(+:e_T) do i = 1, 2*nocc do j = 1, 2*nocc do k = 1, 2*nocc @@ -854,15 +854,15 @@ subroutine do_ccsd_t(sys, int_store) tmp_t3c(a,b,c) = 0.0_p do f = 2*nocc+1, 2*nbasis tmp_t3c(a,b,c) = tmp_t3c(a,b,c) & - + t2(j,k,a,f)*asym(f,i,b,c) - t2(i,k,a,f)*asym(f,j,b,c) - t2(j,i,a,f)*asym(f,k,b,c) & - - t2(j,k,b,f)*asym(f,i,a,c) + t2(i,k,b,f)*asym(f,j,a,c) + t2(j,i,b,f)*asym(f,k,a,c) & - - t2(j,k,c,f)*asym(f,i,b,a) + t2(i,k,c,f)*asym(f,j,b,a) + t2(j,i,c,f)*asym(f,k,b,a) + + t2(k,j,f,a)*asym(f,i,b,c) - t2(k,i,f,a)*asym(f,j,b,c) - t2(i,j,f,a)*asym(f,k,b,c) & + - t2(k,j,f,b)*asym(f,i,a,c) + t2(k,i,f,b)*asym(f,j,a,c) + t2(i,j,f,b)*asym(f,k,a,c) & + - t2(k,j,f,c)*asym(f,i,b,a) + t2(k,i,f,c)*asym(f,j,b,a) + t2(i,j,f,c)*asym(f,k,b,a) end do do m = 1, 2*nocc tmp_t3c(a,b,c) = tmp_t3c(a,b,c) & - - t2(i,m,b,c)*asym(m,a,j,k) + t2(j,m,b,c)*asym(m,a,i,k) + t2(k,m,b,c)*asym(m,a,j,i) & - + t2(i,m,a,c)*asym(m,b,j,k) - t2(j,m,a,c)*asym(m,b,i,k) - t2(k,m,a,c)*asym(m,b,j,i) & - + t2(i,m,b,a)*asym(m,c,j,k) - t2(j,m,b,a)*asym(m,c,i,k) - t2(k,m,b,a)*asym(m,c,j,i) + - t2(m,i,c,b)*asym(m,a,j,k) + t2(m,j,c,b)*asym(m,a,i,k) + t2(m,k,c,b)*asym(m,a,j,i) & + + t2(m,i,c,a)*asym(m,b,j,k) - t2(m,j,c,a)*asym(m,b,i,k) - t2(m,k,c,a)*asym(m,b,j,i) & + + t2(m,i,a,b)*asym(m,c,j,k) - t2(m,j,a,b)*asym(m,c,i,k) - t2(m,k,a,b)*asym(m,c,j,i) end do tmp_t3c_d(a,b,c) = tmp_t3c(a,b,c)/(e(i)+e(j)+e(k)-e(a)-e(b)-e(c)) end do diff --git a/src/hf.f90 b/src/hf.f90 index cfeccd1..e95d9ff 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -45,33 +45,54 @@ subroutine do_hartree_fock(sys, int_store) allocate(st%density_old(sys%nbasis,sys%nbasis), source=0.0_p) - ! Build the orthogonalisation matrix S^-1/2 + ! ############################################ + ! Build the symmetric orthogonalisation matrix + ! ############################################ + ! X = S^-1/2 = U s^{-1/2} U^{\dagger} (Szabo and Ostlund eq. 3.167) ! Initialise the overlap matrix stored in int_store_t into a mat_t object call init_mat_t(int_store%ovlp, ovlp) + ! We're borrowing this from the SCF diagonalisation type, where the init_mat_t puts ovlp into ao but + ! it's ao_ort that gets passed into BLAS for diagonalisation ovlp%ao_ort = ovlp%ao - - ! S^(-1/2) = C * L^(-1/2) * C^(T) call diagonalise(ovlp) - call build_ortmat(ovlp, ortmat) - + ortmat(:,:) = 0.0_p + ! ovlp%W holds the eigenvalues s_i of S + associate(diag=>ovlp%W) + do i = 1, size(ortmat, dim=1) + ortmat(i,i) = 1/sqrt(diag(i)) + end do + end associate + ! S^-1/2 = U s^{-1/2} U^{\dagger}, the coefficient matrix U is held in ovlp%A + ortmat = matmul(ovlp%A, matmul(ortmat, transpose(ovlp%A))) call deallocate_mat_t(ovlp) - ! Initial guess Fock matrix is H_core - ! F'_0 = S^T(-1/2) * F * S^(-1/2) + ! ############################### + ! Various initialisation routines + ! ############################### + ! Initial guess Fock matrix is H_core (equivalent to guessing the null matrix for density matrix) + ! (Szabo and Ostlund p. 148) call init_mat_t(int_store%core_hamil, fockmat) - call init_diis_t(sys, diis) + ! #################### + ! Iterative SCF solver + ! #################### + do iter = 1, maxiter + ! F' is the fock matrix in orthogonal AO basis, where F is in the original non-orthogonal basis + ! F' = X^T F X fockmat%ao_ort = matmul(transpose(ortmat), matmul(fockmat%ao, ortmat)) + ! F'C' = C'e call diagonalise(fockmat) - ! Transform coefficient into nonorthogonal AO basis + ! C = XC' fockmat%A = transpose(matmul(ortmat, fockmat%A)) + ! D_{\mu\nu} = \sum_{i}^{nocc} C_\mu^i C_\nu^i call build_density(fockmat%A, density, sys%nel/2) + ! E_el = \sum_{\mu\nu} D_{\mu\nu} (H^{core}_{\mu\nu} + F_{\mu\nu}) call update_scf_energy(sys, density, fockmat%ao, st, int_store, conv) if (conv) then write(iunit, '(1X, A)') 'Convergence reached within tolerance.' @@ -218,31 +239,6 @@ subroutine deallocate_mat_t(mat) deallocate(mat%W) end subroutine deallocate_mat_t - subroutine build_ortmat(ovlp, ortmat) - - use linalg, only: mat_t - - type(mat_t), intent(in) :: ovlp - real(p), intent(out) :: ortmat(:,:) - - real(p) :: tmpmat(size(ortmat, dim=1), size(ortmat, dim=1)) - - integer :: i - - tmpmat(:,:) = 0.0_p - ortmat(:,:) = 0.0_p - - associate(diag=>ovlp%W) - do i = 1, size(ortmat, dim=1) - ortmat(i,i) = 1/sqrt(diag(i)) - end do - end associate - - tmpmat = matmul(ortmat, transpose(ovlp%A)) - ortmat = matmul(ovlp%A, tmpmat) - - end subroutine build_ortmat - subroutine build_density(coeff, density, nocc) real(p), intent(in) :: coeff(:,:) integer, intent(in) :: nocc diff --git a/src/main.F90 b/src/main.F90 index 4eb2f72..b861aa2 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -3,7 +3,7 @@ program main use const use omp_lib use integrals, only: read_integrals_in, print_sys_info, int_store_t - use system, only: system_t + use system, only: system_t, read_system_in use hf, only: do_hartree_fock use geometry, only: read_geometry_in use mp2, only: do_mp2 @@ -30,6 +30,7 @@ program main call system_clock(t0, count_rate, count_max) + call read_system_in(sys) call read_integrals_in(sys, int_store) call read_geometry_in(sys, int_store) call print_sys_info(sys, int_store) @@ -77,4 +78,4 @@ program main write(iunit, '(1X, A, 1X, I2.2, "/", I2.2, "/", I4.4, 1X, A, 1X, I2.2, 2(":", I2.2))') & "Finished running on", date_values(3:1:-1), "at", date_values(5:7) -end program main \ No newline at end of file +end program main diff --git a/src/system.f90 b/src/system.f90 index f57d3d7..14e55f8 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -34,6 +34,9 @@ module system real(p) :: ccsd_e_tol = 1e-6 real(p) :: ccsd_t_tol = 1e-6 + ! Level of theory (up to) + character(:), allocatable :: calc_type + end type system_t type state_t @@ -44,4 +47,37 @@ module system real(p), allocatable :: t2_old(:,:,:,:) end type state_t -end module system \ No newline at end of file + contains + subroutine read_system_in(sys) + ! Reads in input file called `els.in` in `dat/` specifying the levels of theory and tolerance + ! In/out: + ! sys: system under study + + use error_handling, only: error + type(system_t), intent(inout) :: sys + real(p) :: scf_e_tol, scf_d_tol, ccsd_e_tol, ccsd_t_tol + character(40) :: calc_type + + integer :: ir, ierr + + ! Define namelist + namelist /elsinput/ calc_type, scf_e_tol, scf_d_tol, ccsd_e_tol, ccsd_t_tol + + ! Check if file exists + inquire(file='dat/els.in', iostat=ierr) + if (ierr /= 0) call error('system::read_system_in', 'input file dat/els.in does not exist') + + ! Read namelist + open(newunit=ir, file='dat/els.in', action='read') + read(unit=ir, nml=elsinput, iostat=ierr) + + if (ierr /= 0) call error('system::read_system_in', 'invalid input file format!') + + close(ir) + + sys%calc_type = trim(calc_type); sys%scf_e_tol = scf_e_tol; sys%scf_d_tol = scf_d_tol + sys%ccsd_e_tol = ccsd_e_tol; sys%ccsd_t_tol = ccsd_t_tol + + end subroutine + +end module system From 7da41074f63be2fa5218833d0b6045d44fbc42a6 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 17 Jan 2022 21:53:07 +0000 Subject: [PATCH 45/71] Implement (small-time) modularisation via input file, add spatial and UHF subroutines (now just duplicates of existing subroutines) for future development --- src/ccsd.f90 | 262 ++++++++++++++++++++++++++++++++++++++++++++++++- src/hf.f90 | 22 +++-- src/main.F90 | 88 ++++++++++++----- src/mp2.f90 | 186 ++++++++++++++++++++++++++++++++++- src/system.f90 | 29 +++++- 5 files changed, 545 insertions(+), 42 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 684679c..abf0da6 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -52,7 +52,7 @@ module ccsd contains - subroutine do_ccsd(sys, int_store) + subroutine do_ccsd_spinorb(sys, int_store) ! This is the spinorbital formulation of J.F. Stanton, J. Gauss, J.D. Watts, and R.J. Bartlett, J. Chem. Phys. volume 94, pp. 4334-4345 (1991) (https://doi.org/10.1063/1.460620) ! [TODO]: closed-shell (spatial) formulation of Hirata, S.; Podeszwa, R.; Tobita, M.; Bartlett, R. J. J. Chem. Phys. 2004, 120 (6), 2581 (https://doi.org/10.1063/1.1637577) @@ -211,7 +211,169 @@ subroutine do_ccsd(sys, int_store) call deallocate_cc_int_t(cc_int) call deallocate_diis_cc_t(diis) - end subroutine do_ccsd + end subroutine do_ccsd_spinorb + + subroutine do_ccsd_spatial(sys, int_store) + ! This is the spinorbital formulation of J.F. Stanton, J. Gauss, J.D. Watts, and R.J. Bartlett, J. Chem. Phys. volume 94, pp. 4334-4345 (1991) (https://doi.org/10.1063/1.460620) + ! [TODO]: closed-shell (spatial) formulation of Hirata, S.; Podeszwa, R.; Tobita, M.; Bartlett, R. J. J. Chem. Phys. 2004, 120 (6), 2581 (https://doi.org/10.1063/1.1637577) + + use integrals, only: int_store_t, eri_ind + use error_handling, only: error, check_allocate + use system, only: state_t + + type(system_t), intent(inout) :: sys + type(int_store_t), intent(inout) :: int_store + integer :: i, j, a, b, p, q, r, s + integer :: pr, qr, pa, pb, qa, qb, ra, rb, sa, sb + real(dp) :: prqs, psqr + real(dp) :: err + integer(kind=8) :: c_max, c_rate, t0, t1 + + type(state_t) :: st + type(diis_cc_t) :: diis + + type(cc_amp_t) :: cc_amp + integer :: ierr, iter + integer, parameter :: iunit = 6 + integer, parameter :: maxiter = 100 + + type(cc_int_t) :: cc_int + logical :: conv + + write(iunit, '(1X, 10("-"))') + write(iunit, '(1X, A)') 'CCSD' + write(iunit, '(1X, 10("-"))') + + ! ############################################################################# + ! Form the antisymmetrised spinorbital basis ERIs: = - + ! where = (pr|qs) * delta(sigma_p,sigma_r) * delta(sigma_q,sigma_s) + ! ############################################################################# + write(iunit, '(1X, A)') 'Forming antisymmetrised spinorbital ERIs...' + call system_clock(count=t0, count_rate=c_rate, count_max=c_max) + allocate(int_store%asym_spinorb(sys%nbasis*2,sys%nbasis*2,sys%nbasis*2,sys%nbasis*2), source=0.0_dp, stat=ierr) + call check_allocate('int_store%asym_spinorb', sys%nbasis**4*16, ierr) + + associate(n=>sys%nbasis, asym=>int_store%asym_spinorb, eri=>int_store%eri_mo) + ! [TODO]: this isn't necessary but easier for debugging, change to spin lookup arrays or something similar + do p = 1, n + pa = 2*p-1 + pb = pa+1 + + do q = 1, n + qa = 2*q-1 + qb = qa+1 + + do r = 1, n + ra = 2*r-1 + rb = ra+1 + + pr = eri_ind(p,r) + qr = eri_ind(q,r) + + do s = 1, n + sa = 2*s-1 + sb = sa+1 + prqs = eri(eri_ind(pr,eri_ind(q,s))) + psqr = eri(eri_ind(eri_ind(p,s),qr)) + ! Draw a spin decision tree to visualise + asym(pa,qa,ra,sa) = prqs-psqr + asym(pb,qb,rb,sb) = prqs-psqr + asym(pa,qb,ra,sb) = prqs + asym(pb,qa,rb,sa) = prqs + asym(pa,qb,rb,sa) = -psqr + asym(pb,qa,ra,sb) = -psqr + end do + end do + end do + end do + end associate + call system_clock(t1) + if (t1sys%nbasis, asym=>int_store%asym_spinorb) + do p = 1, 2*nbasis + do q = 1, p + do r = 1, p + do s = 1, min(r,p) + err = err + abs(asym(p,q,r,s) + asym(p,q,s,r)) + abs(asym(p,q,r,s) - asym(r,s,p,q)) & + + abs(asym(p,q,r,s) + asym(s,r,p,q)) + abs(asym(p,q,r,s) - asym(s,r,q,p)) + end do + end do + end do + end do + end associate + + if (err > depsilon) then + write(iunit, '(1X, A, 1X, E15.6)') 'Permutational symmetry error:', err + call error('ccsd::do_ccsd', 'Permutational symmetry of antisymmetrised integrals does not hold') + end if + + call system_clock(t1) + if (t1sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab, asym=>int_store%asym_spinorb) + do iter = 1, maxiter + ! Update intermediate tensors + call build_tau(sys, cc_amp, cc_int) + call build_F(sys, cc_int, cc_amp, asym) + call build_W(sys, cc_int, cc_amp, asym) + + ! CC amplitude equations + call update_amplitudes(sys, cc_amp, int_store, cc_int) + call update_cc_energy(sys, st, int_store, cc_amp, conv) + + if (conv) then + write(iunit, '(1X, A)') 'Convergence reached within tolerance.' + write(iunit, '(1X, A, 1X, F15.8)') 'Final CCSD Energy (Hartree):', st%energy + + ! Copied for return + sys%e_ccsd = st%energy + call move_alloc(cc_amp%t_ia, sys%t1) + call move_alloc(cc_amp%t_ijab, sys%t2) + exit + end if + call update_diis_cc(diis, cc_amp) + + call system_clock(t1) + write(iunit, '(1X, A, 1X, I2, 2X, F10.7, 2X, F8.6, 1X, A)') 'Iteration', iter, st%energy,real(t1-t0, kind=dp)/c_rate,'s' + t0=t1 + end do + end associate + + ! Nonlazy deallocations + deallocate(st%t2_old) + call deallocate_cc_int_t(cc_int) + call deallocate_diis_cc_t(diis) + + + end subroutine do_ccsd_spatial subroutine init_cc(sys, int_store, cc_amp, cc_int) ! Initialise many CC related quantities. @@ -792,7 +954,96 @@ subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) end subroutine update_cc_energy - subroutine do_ccsd_t(sys, int_store) + subroutine do_ccsd_t_spinorb(sys, int_store) + ! Spinorbital formuation of CCSD(T) + ! In: + ! int_store: integral information. + ! In/out: + ! sys: holds converged amplitudes from CCSD + + use integrals, only: int_store_t + use error_handling, only: check_allocate + + type(system_t), intent(inout) :: sys + type(int_store_t), intent(in) :: int_store + + integer :: i, j, k, a, b, c, f, m, ierr + real(p), allocatable :: tmp_t3d(:,:,:), tmp_t3c(:,:,:), tmp_t3c_d(:,:,:) + real(p) :: e_T + integer, parameter :: iunit = 6 + + write(iunit, '(1X, 10("-"))') + write(iunit, '(1X, A)') 'CCSD(T)' + write(iunit, '(1X, 10("-"))') + + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, e=>sys%canon_levels_spinorb, t1=>sys%t1, t2=>sys%t2,& + asym=>int_store%asym_spinorb) + !$omp parallel default(none) & + !$omp private(i, j, k, a, b, c, f, m, tmp_t3d, tmp_t3c, tmp_t3c_d, ierr) & + !$omp shared(sys, int_store, e_T) + e_T = 0.0_p + + ! Declare heap-allocated arrays inside parallel region + allocate(tmp_t3d(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) + call check_allocate('tmp_t3d', 8*(nbasis-nocc)**3, ierr) + allocate(tmp_t3c(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) + call check_allocate('tmp_t3c', 8*(nbasis-nocc)**3, ierr) + allocate(tmp_t3c_d(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) + call check_allocate('tmp_t3c_d', 8*(nbasis-nocc)**3, ierr) + + ! We use avoid the storage of full triples (six-dimensional array..) and instead use the strategy of + ! batched triples storage, denoted W^{ijk}(abc) in (https://doi.org/10.1016/0009-2614(91)87003-T). + ! We could of course only compute one element in a loop iteration but that will probably result in bad floating point + ! performance, here for each thread/loop iteration we use the Fortran intrinsic sum, + ! instead of all relying on OMP reduction, to hopefully give better floating point performance. + !$omp do schedule(runtime) collapse(3) reduction(+:e_T) + do i = 1, 2*nocc + do j = 1, 2*nocc + do k = 1, 2*nocc + ! Compute T3 amplitudes + do a = 2*nocc+1, 2*nbasis + do b = 2*nocc+1, 2*nbasis + do c = 2*nocc+1, 2*nbasis + ! Disonnected T3: D_{ijk}^{abc}*t_{ijk}^{abc}(d) = P(i/jk)P(a/bc)t_i^a* + ! Can be rewritten directly as no sums in the expression + tmp_t3d(a,b,c) = - t1(i,a)*asym(c,b,j,k) + t1(j,a)*asym(c,b,i,k) + t1(k,a)*asym(c,b,j,i) & + + t1(i,b)*asym(c,a,j,k) - t1(j,b)*asym(c,a,i,k) - t1(k,b)*asym(c,a,j,i) & + - t1(i,c)*asym(j,k,b,a) + t1(j,c)*asym(i,k,b,a) + t1(k,c)*asym(j,i,b,a) + tmp_t3d(a,b,c) = tmp_t3d(a,b,c)/(e(i)+e(j)+e(k)-e(a)-e(b)-e(c)) + + ! Connected T3: D_{ijk}^{abc}*t_{ijk}^{abc}(c) = P(i/jk)P(a/bc)[\sum_f t_jk^af - \sum_m t_im^bc ] + ! Has to be zeroed as all terms are sums + tmp_t3c(a,b,c) = 0.0_p + do f = 2*nocc+1, 2*nbasis + tmp_t3c(a,b,c) = tmp_t3c(a,b,c) & + + t2(k,j,f,a)*asym(f,i,b,c) - t2(k,i,f,a)*asym(f,j,b,c) - t2(i,j,f,a)*asym(f,k,b,c) & + - t2(k,j,f,b)*asym(f,i,a,c) + t2(k,i,f,b)*asym(f,j,a,c) + t2(i,j,f,b)*asym(f,k,a,c) & + - t2(k,j,f,c)*asym(f,i,b,a) + t2(k,i,f,c)*asym(f,j,b,a) + t2(i,j,f,c)*asym(f,k,b,a) + end do + do m = 1, 2*nocc + tmp_t3c(a,b,c) = tmp_t3c(a,b,c) & + - t2(m,i,c,b)*asym(m,a,j,k) + t2(m,j,c,b)*asym(m,a,i,k) + t2(m,k,c,b)*asym(m,a,j,i) & + + t2(m,i,c,a)*asym(m,b,j,k) - t2(m,j,c,a)*asym(m,b,i,k) - t2(m,k,c,a)*asym(m,b,j,i) & + + t2(m,i,a,b)*asym(m,c,j,k) - t2(m,j,a,b)*asym(m,c,i,k) - t2(m,k,a,b)*asym(m,c,j,i) + end do + tmp_t3c_d(a,b,c) = tmp_t3c(a,b,c)/(e(i)+e(j)+e(k)-e(a)-e(b)-e(c)) + end do + end do + end do + + ! Calculate contributions + e_T = e_T + sum(tmp_t3c*(tmp_t3c_d+tmp_t3d))/36 + end do + end do + end do + !$omp end do + !$omp end parallel + sys%e_ccsd_t = e_T + write(iunit, '(1X, A, 1X, F15.9)') 'CCSD(T) correlation energy (Hartree):', e_T + end associate + end subroutine do_ccsd_t_spinorb + + subroutine do_ccsd_t_spatial(sys, int_store) ! Spinorbital formuation of CCSD(T) ! In: ! int_store: integral information. @@ -879,5 +1130,6 @@ subroutine do_ccsd_t(sys, int_store) sys%e_ccsd_t = e_T write(iunit, '(1X, A, 1X, F15.9)') 'CCSD(T) correlation energy (Hartree):', e_T end associate - end subroutine do_ccsd_t -end module ccsd \ No newline at end of file + end subroutine do_ccsd_t_spatial + +end module ccsd diff --git a/src/hf.f90 b/src/hf.f90 index e95d9ff..b8154f9 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -16,11 +16,11 @@ module hf end type diis_t contains - subroutine do_hartree_fock(sys, int_store) - use error_handling - use system - use integrals - use linalg + subroutine do_rhf(sys, int_store) + use error_handling, only: error + use system, only: system_t, state_t + use integrals, only: int_store_t + use linalg, only: mat_t type(int_store_t), intent(in) :: int_store type(system_t), intent(inout) :: sys @@ -39,9 +39,9 @@ subroutine do_hartree_fock(sys, int_store) iunit = 6 maxiter = 100 - write(iunit, '(1X, 12("-"))') - write(iunit, '(1X, A)') 'Hartree-Fock' - write(iunit, '(1X, 12("-"))') + write(iunit, '(1X, 23("-"))') + write(iunit, '(1X, A)') 'Restricted Hartree-Fock' + write(iunit, '(1X, 23("-"))') allocate(st%density_old(sys%nbasis,sys%nbasis), source=0.0_p) @@ -123,7 +123,11 @@ subroutine do_hartree_fock(sys, int_store) call deallocate_diis_t(diis) deallocate(st%density_old) - end subroutine do_hartree_fock + end subroutine do_rhf + + subroutine do_uhf + continue + end subroutine do_uhf subroutine update_diis(diis, fock, density, ovlp) use linalg, only: linsolve diff --git a/src/main.F90 b/src/main.F90 index b861aa2..e0265f9 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -4,10 +4,11 @@ program main use omp_lib use integrals, only: read_integrals_in, print_sys_info, int_store_t use system, only: system_t, read_system_in - use hf, only: do_hartree_fock + use system, only: RHF, UHF, MP2_spinorb, MP2_spatial, CCSD_spinorb, CCSD_spatial, CCSD_T_spinorb, CCSD_T_spatial + use hf, only: do_rhf, do_uhf use geometry, only: read_geometry_in - use mp2, only: do_mp2 - use ccsd, only: do_ccsd, do_ccsd_t + use mp2, only: do_mp2_spinorb, do_mp2_spatial + use ccsd, only: do_ccsd_spinorb, do_ccsd_spatial, do_ccsd_t_spinorb, do_ccsd_t_spatial implicit none @@ -34,34 +35,75 @@ program main call read_integrals_in(sys, int_store) call read_geometry_in(sys, int_store) call print_sys_info(sys, int_store) + call system_clock(t1) if (t1sys%calc_type) + if (any((/ct==MP2_spinorb, ct==CCSD_spinorb, ct==CCSD_T_spinorb/))) then + ! Currently UHF is not implemented, so we convert spatial HF orbitals into spinorbitals + call do_rhf(sys, int_store) + call system_clock(t1) + if (t1sys%canon_coeff, eri_mo=>int_store%eri_mo, eri=>int_store%eri) + !$omp do schedule(dynamic, 2) collapse(2) + + ! Naively (see above) we can perform the transformation of (ij|kl)->(pq|rs) in an O(N^8) loop: + ! do ijklpqrs + ! (pq|rs) = C_pi C_qj C_rk C_sl (ij|kl) + ! end do + ! + ! But we can also, with the aid of two 4-dimensional temp matrices, perform 4 O(N^5) loops: + ! do ijklp + ! (pj|kl) (tmp_a) += (ij|kl) * C_pi + ! end do + ! do pjklq + ! (pq|kl) (tmp_b) += (pj|kl) (tmp_a) * C_qj + ! end do + ! do pqklr + ! (pq|rl) (tmp_a) += (pq|kl) (tmp_b) * C_rk + ! end do + ! do pqrls + ! (pq|rs) (tmp_b) += (pq|rl) (tmp_a) * C_sl + ! end do + ! + ! One last loop to store in one dimensional array with perm. symmetry... + + ! Notice the order of the loops are optimised for Fortran coloumn major array storage: + ! the first index varies the fastest etc. + + ! (ij|kl) -> (pj|kl) + do l = 1, n + do k = 1, n + kl = eri_ind(k,l) + do i = 1, n + do j = 1, n + ij = eri_ind(i,j) + do p = 1, n + tmp_a(p,j,k,l) = tmp_a(p,j,k,l) + eri(eri_ind(ij,kl))*C(p,i) + end do + end do + end do + end do + end do + !$omp end do + + !$omp do schedule(dynamic, 2) collapse(2) + ! (pj|kl) -> (pq|kl) + do l = 1, n + do k = 1, n + do j = 1, n + do q = 1, n + do p = 1, n + tmp_b(p,q,k,l) = tmp_b(p,q,k,l) + tmp_a(p,j,k,l)*C(q,j) + end do + end do + end do + end do + end do + !$omp end do + + ! (pq|kl) -> (pq|rl) + !$omp single + tmp_a(:,:,:,:) = 0.0_dp + !$omp end single + + !$omp do schedule(dynamic, 2) collapse(2) + do l = 1, n + do r = 1, n + do k = 1, n + do q = 1, n + do p = 1, n + tmp_a(p,q,r,l) = tmp_a(p,q,r,l) + tmp_b(p,q,k,l)*C(r,k) + end do + end do + end do + end do + end do + !$omp end do + + ! (pq|rl) -> (pq|rs) + !$omp single + tmp_b(:,:,:,:) = 0.0_dp + !$omp end single + !$omp do schedule(dynamic, 2) collapse(2) + do s = 1, n + do r = 1, n + do l = 1, n + do q = 1, n + do p = 1, n + tmp_b(p,q,r,s) = tmp_b(p,q,r,s) + tmp_a(p,q,r,l)*C(s,l) + end do + end do + end do + end do + end do + !$omp end do + + !$omp single + pq = 0 + pqrs = 0 + do p = 1, n + do q = 1, p + pq = pq + 1 + do r = 1, p + if (p==r) then + ! If p==r, then s must be smaller than q for rs <= pq + s_up = q + else + ! Default rules + s_up = r + end if + do s = 1, s_up + pqrs = pqrs + 1 + ! use full permutational symmetry to optimise cache behaviour + eri_mo(pqrs) = tmp_b(s,r,q,p) + end do + end do + end do + end do + !$omp end single + end associate + !$omp end parallel + + + deallocate(tmp_a, tmp_b) + write(iunit, '(1X, A)') 'Calculating MP2 energy...' + + nocc = sys%nel/2 + associate(e=>sys%canon_levels, eri=>int_store%eri_mo, emp=>sys%e_mp2) + emp = 0.0_dp + do i = 1, nocc + do j = 1, nocc + do a = nocc+1, n + ia = eri_ind(i,a) + ja = eri_ind(j,a) + do b = nocc+1, n + jb = eri_ind(j,b) + ib = eri_ind(i,b) + emp = emp+(eri(eri_ind(ia,jb))*(2*eri(eri_ind(ia,jb))-eri(eri_ind(ib,ja))))& + / (e(i)+e(j)-e(a)-e(b)) + end do + end do + end do + end do + end associate + + write(iunit, '(1X, A, 1X, F15.8)') 'MP2 correlation energy (Hartree):', sys%e_mp2 + + end subroutine do_mp2_spatial + +end module mp2 diff --git a/src/system.f90 b/src/system.f90 index 14e55f8..c9278f6 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -3,6 +3,10 @@ module system implicit none + enum, bind(c) + enumerator :: RHF, UHF, MP2_spinorb, MP2_spatial, CCSD_spinorb, CCSD_spatial, CCSD_T_spinorb, CCSD_T_spatial + end enum + type system_t ! Basic system information integer :: nel = 0 @@ -35,7 +39,7 @@ module system real(p) :: ccsd_t_tol = 1e-6 ! Level of theory (up to) - character(:), allocatable :: calc_type + integer :: calc_type end type system_t @@ -75,9 +79,30 @@ subroutine read_system_in(sys) close(ir) - sys%calc_type = trim(calc_type); sys%scf_e_tol = scf_e_tol; sys%scf_d_tol = scf_d_tol + sys%scf_e_tol = scf_e_tol; sys%scf_d_tol = scf_d_tol sys%ccsd_e_tol = ccsd_e_tol; sys%ccsd_t_tol = ccsd_t_tol + select case(trim(calc_type)) + case("RHF") + sys%calc_type = RHF + case("UHF") + sys%calc_type = UHF + case("MP2_spinorb") + sys%calc_type = MP2_spinorb + case("MP2_spatial") + sys%calc_type = MP2_spatial + case("CCSD_spinorb") + sys%calc_type = CCSD_spinorb + case("CCSD_spatial") + sys%calc_type = CCSD_spatial + case("CCSD(T)_spinorb") + sys%calc_type = CCSD_T_spinorb + case("CCSD(T)_spatial") + sys%calc_type = CCSD_T_spatial + case default + call error('system::read_system_in', 'Unrecognised calculation type!') + end select + end subroutine end module system From fd23bf8b526bb821bbede902385065e901638881 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Tue, 18 Jan 2022 15:31:56 +0000 Subject: [PATCH 46/71] Update README.md with compilation instructions --- README.md | 21 +++++++++++++++++++++ 1 file changed, 21 insertions(+) diff --git a/README.md b/README.md index 8c68fb0..b54180f 100644 --- a/README.md +++ b/README.md @@ -23,3 +23,24 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [ ] MPI parallelisation - [ ] GPU adaptation for MP2 and CCSD/(T) - [ ] User input file: level of theory, tolerances + +## Installation guide +To get started, clone this directory by +``` +git clone git@github.com:brianz98/A-Fortran-Electronic-Structure-Programme.git +``` +### Dependencies +You need to have: +- CMake (at least 3.12) +- A Fortran compiler (gfortran 9.3.0 have been tested) +- OpenBLAS (see below for instructions) + +### Installing OpenBLAS +Download the latest OpenBLAS version from [their website](https://www.openblas.net/), and untar, then +``` +make USE_OPENMP=1 +make install [PREFIX=/your/directory] +``` +where the `PREFIX` can be omitted and OpenBLAS will be installed in `/opt/OpenBLAS` by default, but you'll likely need to prefix `sudo` to the command. + +If you install OpenBLAS in directories other than `/opt/OpenBLAS`, then you need to edit the last line of `CMakeLists.txt` to where `libopenblas.a` actually is. From 50778c20869781ff295e78d07352d2456debb0e2 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sun, 23 Jan 2022 17:45:44 +0000 Subject: [PATCH 47/71] Add dgemm wrapper, will update the already-functional spinorbital formulations directly in master --- src/linalg.f90 | 12 ++++++++++++ 1 file changed, 12 insertions(+) diff --git a/src/linalg.f90 b/src/linalg.f90 index 9085ef2..306632a 100644 --- a/src/linalg.f90 +++ b/src/linalg.f90 @@ -55,6 +55,18 @@ subroutine linsolve(A, B, ierr) end subroutine linsolve + subroutine dgemm_wrapper(transA, transB, outer_row, outer_col, inner_dim, A, B, C) + ! Wraps around dgemm with fewer arguments + + character(1), intent(in) :: transA, transB + integer, intent(in) :: outer_row, outer_col, inner_dim + real(p), intent(in) :: A(*), B(*) + real(p), intent(inout) :: C(*) + + call dgemm(transA, transB, outer_row, outer_col, inner_dim, 1.0_dp, & + A, outer_row, B, inner_dim, 0.0_dp, C, outer_row) + end subroutine dgemm_wrapper + elemental subroutine zero_mat(matel) ! Zero out entries smaller than machine precision From 128230f935e2099b56a1fb0f51f3f90fbd560019 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 24 Jan 2022 11:21:04 +0000 Subject: [PATCH 48/71] First attempt at dgemm, good results (~2x faster on water/DZP), rate limiting steps are due to asymmetrised integrals, need to make slices of them next. --- src/ccsd.f90 | 103 ++++++++++++++++++++++++++++----------------------- 1 file changed, 57 insertions(+), 46 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index abf0da6..2cdc223 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -604,7 +604,7 @@ subroutine build_tau(sys, cc_amp, cc_int) !$omp parallel do default(none) & !$omp private(i,j,a,b,ia,ja,x) & !$omp shared(sys, cc_amp, cc_int) & - !$omp schedule(runtime) collapse(2) + !$omp schedule(static, 10) collapse(2) do b = 2*nocc+1, 2*n do a = 2*nocc+1, 2*n do j = 1, 2*nocc @@ -641,7 +641,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& F_vv=>cc_int%F_vv, F_oo=>cc_int%F_oo, F_ov=>cc_int%F_ov, tau_tilde=>cc_int%tau_tilde) - ! F_ae = \sum_{mf} t_m^f * - 0.5 \sum_{mnf} \tau~_{mn}^{af} + F_vv = 0.0_p F_oo = 0.0_p F_ov = 0.0_p @@ -650,7 +650,8 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp private(a, e, f, m, n, i) & !$omp shared(sys, cc_int, cc_amp, asym) - !$omp do schedule(runtime) collapse(2) + ! F_ae = \sum_{mf} t_m^f * - 0.5 \sum_{mnf} \tau~_{mn}^{af} + !$omp do schedule(static, 10) collapse(2) do a = 2*nocc+1, 2*nbasis do e = 2*nocc+1, 2*nbasis do m = 1, 2*nocc @@ -666,7 +667,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp end do ! F_mi = \sum_{en} t_n^e + 0.5 \sum_{nef} \tau~_{in}^{ef} - !$omp do schedule(runtime) collapse(2) + !$omp do schedule(static, 10) collapse(2) do m = 1, 2*nocc do i = 1, 2*nocc do e = 2*nocc+1, 2*nbasis @@ -682,7 +683,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp end do ! F_me = \sum_{nf} t_n^f * - !$omp do schedule(runtime) collapse(2) + !$omp do schedule(static, 10) collapse(2) do m = 1, 2*nocc do e = 2*nocc+1, 2*nbasis do n = 1, 2*nocc @@ -724,16 +725,18 @@ subroutine build_W(sys, cc_int, cc_amp, asym) !$omp private(m, n, i, j, e, f, b, x, a) & !$omp shared(sys, cc_int, cc_amp, asym) - !$omp do schedule(runtime) collapse(4) - do m = 1, 2*nocc - do n = 1, 2*nocc - do i = 1, 2*nocc - do j = 1, 2*nocc - W_oooo(m,n,i,j) = asym(m,n,i,j) + ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed + ! by a simple dgemm call + !$omp do schedule(static, 10) collapse(4) + do n = 1, 2*nocc + do m = 1, 2*nocc + do j = 1, 2*nocc + do i = 1, 2*nocc + W_oooo(i,j,m,n) = asym(i,j,m,n) do e = 2*nocc+1, 2*nbasis - W_oooo(m,n,i,j) = W_oooo(m,n,i,j) + t_ia(j,e)*asym(e,i,n,m) - t_ia(i,e)*asym(e,j,n,m) + W_oooo(i,j,m,n) = W_oooo(i,j,m,n) + t_ia(j,e)*asym(e,i,n,m) - t_ia(i,e)*asym(e,j,n,m) do f = 2*nocc+1, 2*nbasis - W_oooo(m,n,i,j) = W_oooo(m,n,i,j) - 0.5*t_ijab(j,i,f,e)*asym(f,e,m,n) + W_oooo(i,j,m,n) = W_oooo(i,j,m,n) - 0.5*t_ijab(j,i,f,e)*asym(f,e,m,n) end do end do end do @@ -743,14 +746,15 @@ subroutine build_W(sys, cc_int, cc_amp, asym) !$omp end do ! [TODO]: make a switch to on-the-fly W_vvvv computation, for when memory is limited - !$omp do schedule(runtime) collapse(4) - do f = 2*nocc+1, 2*nbasis - do e = 2*nocc+1, 2*nbasis - do b = 2*nocc+1, 2*nbasis - do a = 2*nocc+1, 2*nbasis - W_vvvv(a,b,e,f) = asym(a,b,e,f) + ! Similarly, we order it (e,f,a,b) for the contraction tau_ij^ef W_abef + !$omp do schedule(static, 10) collapse(4) + do b = 2*nocc+1, 2*nbasis + do a = 2*nocc+1, 2*nbasis + do f = 2*nocc+1, 2*nbasis + do e = 2*nocc+1, 2*nbasis + W_vvvv(e,f,a,b) = asym(e,f,a,b) do n = 1, 2*nocc - W_vvvv(a,b,e,f) = W_vvvv(a,b,e,f) + t_ia(n,b)*asym(n,a,e,f) - t_ia(n,a)*asym(n,b,e,f) + W_vvvv(e,f,a,b) = W_vvvv(e,f,a,b) + t_ia(n,b)*asym(n,a,e,f) - t_ia(n,a)*asym(n,b,e,f) end do end do end do @@ -758,7 +762,7 @@ subroutine build_W(sys, cc_int, cc_amp, asym) end do !$omp end do - !$omp do schedule(runtime) collapse(4) + !$omp do schedule(static, 10) collapse(4) do j = 1, 2*nocc do e = 2*nocc+1, 2*nbasis do b = 2*nocc+1, 2*nbasis @@ -795,34 +799,37 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) ! cc_int: CC intermediates used in computing the updates use integrals, only: int_store_t + use linalg, only: dgemm_wrapper type(system_t), intent(in) :: sys type(int_store_t), intent(in) :: int_store type(cc_amp_t), intent(inout) :: cc_amp type(cc_int_t), intent(inout) :: cc_int + real(p), allocatable :: tmp_t2_s(:,:,:,:) + integer :: i, j, a, b, m, n, e, f - + associate(tmp_t1=>cc_int%tmp_tia,tmp_t2=>cc_int%tmp_tijab,t1=>cc_amp%t_ia,t2=>cc_amp%t_ijab,asym=>int_store%asym_spinorb, & F_oo=>cc_int%F_oo,F_ov=>cc_int%F_ov,F_vv=>cc_int%F_vv,D_ia=>cc_int%D_ia,D_ijab=>cc_int%D_ijab,W_oooo=>cc_int%W_oooo, & - W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nbasis=>sys%nbasis,& + W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nbasis=>sys%nbasis,nvirt=>sys%nvirt,& W_vvvv=>cc_int%W_vvvv) ! Update T1 + + tmp_t1 = matmul(t1,transpose(F_vv)) + tmp_t1 = tmp_t1 - matmul(transpose(F_oo),t1) + !$omp parallel default(none) & - !$omp private(i, j, a, b, m, n, e, f) & !$omp shared(sys, cc_amp, int_store, cc_int) ! Implied barrier here, better than master which doesn't have implied barrier ! tmp_t1 can be shared as each loop iteration will update a unique element of it. - !$omp single - tmp_t1 = 0.0_dp - !$omp end single - !$omp do schedule(runtime) collapse(2) + + !$omp do schedule(static, 10) collapse(2) do a = 2*nocc+1, 2*nbasis do i = 1, 2*nocc do m = 1, 2*nocc - tmp_t1(i,a) = tmp_t1(i,a) - t1(m,a)*F_oo(m,i) do e = 2*nocc+1, 2*nbasis tmp_t1(i,a) = tmp_t1(i,a) + t2(m,i,e,a)*F_ov(m,e) do f = 2*nocc+1, 2*nbasis @@ -834,7 +841,6 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do end do do e = 2*nocc+1, 2*nbasis - tmp_t1(i,a) = tmp_t1(i,a) + t1(i,e)*F_vv(a,e) do n = 1, 2*nocc tmp_t1(i,a) = tmp_t1(i,a) - t1(n,e)*asym(n,a,i,e) end do @@ -842,29 +848,25 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do end do !$omp end do + !$omp end parallel - !$omp single tmp_t1 = tmp_t1/D_ia ! Update T2 - tmp_t2 = 0.0_dp - !$omp end single - !$omp do schedule(runtime) collapse(4) + !$omp parallel default(none) & + !$omp shared(sys, cc_amp, int_store, cc_int) + !$omp do schedule(static, 10) collapse(4) do b = 2*nocc+1, 2*nbasis do a = 2*nocc+1, 2*nbasis do j = 1, 2*nocc do i = 1, 2*nocc tmp_t2(i,j,a,b) = asym(i,j,a,b) do e = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + t2(j,i,e,a)*F_vv(b,e) - t2(j,i,e,b)*F_vv(a,e) & + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(j,i,e,b)*F_vv(a,e) & + tmp_t1(i,e)*asym(e,j,a,b) - tmp_t1(j,e)*asym(e,i,a,b) do m = 1, 2*nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,j,a,e)*tmp_t1(m,b)-& - t2(i,j,b,e)*tmp_t1(m,a)) - end do - do f = 2*nocc+1, 2*nbasis - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(j,i,f,e)*W_vvvv(a,b,e,f) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*F_ov(m,e)*t2(i,j,b,e)*tmp_t1(m,a) end do end do do m = 1, 2*nocc @@ -874,9 +876,6 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*tmp_t1(j,e)-& t2(j,m,a,b)*tmp_t1(i,e)) end do - do n = 1, 2*nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*tau(n,m,b,a)*W_oooo(m,n,i,j) - end do end do do m = 1, 2*nocc @@ -894,6 +893,18 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do !$omp end do !$omp end parallel + + allocate(tmp_t2_s, source=t2) + + ! t_ij^ae F_be + call dgemm_wrapper('N','T',8*nocc**2*nvirt,2*nvirt,2*nvirt,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) + tmp_t2 = tmp_t2 + tmp_t2_s + call dgemm_wrapper('N','N',4*nocc**2,4*nvirt**2,4*nocc**2,W_oooo,tau,tmp_t2_s) + tmp_t2 = tmp_t2 + tmp_t2_s/2 + call dgemm_wrapper('N','N',4*nocc**2,4*nvirt**2,4*nvirt**2,tau,W_vvvv,tmp_t2_s) + tmp_t2 = tmp_t2 + tmp_t2_s/2 + deallocate(tmp_t2_s) + t1 = tmp_t1 t2 = tmp_t2/D_ijab end associate @@ -931,7 +942,7 @@ subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) !$omp shared(sys,st,int_store,cc_amp,ecc,rmst2) ecc = 0.0_p rmst2 = 0.0_p - !$omp do schedule(runtime) collapse(4) reduction(+:ecc,rmst2) + !$omp do schedule(static, 10) collapse(4) reduction(+:ecc,rmst2) do b = 2*nocc+1, 2*nbasis do a = 2*nocc+1, 2*nbasis do j = 1, 2*nocc @@ -996,7 +1007,7 @@ subroutine do_ccsd_t_spinorb(sys, int_store) ! We could of course only compute one element in a loop iteration but that will probably result in bad floating point ! performance, here for each thread/loop iteration we use the Fortran intrinsic sum, ! instead of all relying on OMP reduction, to hopefully give better floating point performance. - !$omp do schedule(runtime) collapse(3) reduction(+:e_T) + !$omp do schedule(static, 10) collapse(3) reduction(+:e_T) do i = 1, 2*nocc do j = 1, 2*nocc do k = 1, 2*nocc @@ -1085,7 +1096,7 @@ subroutine do_ccsd_t_spatial(sys, int_store) ! We could of course only compute one element in a loop iteration but that will probably result in bad floating point ! performance, here for each thread/loop iteration we use the Fortran intrinsic sum, ! instead of all relying on OMP reduction, to hopefully give better floating point performance. - !$omp do schedule(runtime) collapse(3) reduction(+:e_T) + !$omp do schedule(static, 10) collapse(3) reduction(+:e_T) do i = 1, 2*nocc do j = 1, 2*nocc do k = 1, 2*nocc From 6d297f678c260b482823bb29c08c7d07683f39bf Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 24 Jan 2022 11:25:34 +0000 Subject: [PATCH 49/71] Update README.md --- README.md | 2 +- 1 file changed, 1 insertion(+), 1 deletion(-) diff --git a/README.md b/README.md index b54180f..a0d08da 100644 --- a/README.md +++ b/README.md @@ -15,6 +15,7 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [X] CCSD(T) without symmetry - [X] DIIS acceleration for CCSD iterations - [X] Loop optimisations - cache +- [X] User input file: level of theory, tolerances - [ ] Loop optimisations - using permutational symmetry - [ ] Adapting Hartree-Fock with symmetry - [ ] Ditto for MP2 @@ -22,7 +23,6 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [ ] Ditto for CCSD(T) - [ ] MPI parallelisation - [ ] GPU adaptation for MP2 and CCSD/(T) -- [ ] User input file: level of theory, tolerances ## Installation guide To get started, clone this directory by From 6c38870b045504d56120be0a17cbe5f559b7939b Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 24 Jan 2022 23:08:35 +0000 Subject: [PATCH 50/71] add untested dgemms with ERI slices --- src/ccsd.f90 | 123 +++++++++++++++++++++++++++++++-------------------- 1 file changed, 74 insertions(+), 49 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 2cdc223..87356af 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -22,6 +22,9 @@ module ccsd ! Energy denominators (Eqs. 12-13) real(dp), allocatable :: D_ia(:,:), D_ijab(:,:,:,:) real(dp), allocatable :: tmp_tia(:,:), tmp_tijab(:,:,:,:) + + ! Various slices of asymmetrised integrals + real(dp), dimension(:,:,:,:), allocatable :: oooo, ovoo, oovo, ooov, oovv, ovov, ovvv, vovv, vvvv, ovvo end type cc_int_t type diis_cc_t @@ -134,7 +137,7 @@ subroutine do_ccsd_spinorb(sys, int_store) write(iunit, '(1X, A)') 'Checking that the permuational symmetry of the antisymmetrised integrals hold...' err = 0.0_dp - associate(nbasis=>sys%nbasis, asym=>int_store%asym_spinorb) + associate(nbasis=>sys%nbasis,nocc=>sys%nocc,nvirt=>sys%nvirt,asym=>int_store%asym_spinorb) do p = 1, 2*nbasis do q = 1, p do r = 1, p @@ -145,8 +148,7 @@ subroutine do_ccsd_spinorb(sys, int_store) end do end do end do - end associate - + if (err > depsilon) then write(iunit, '(1X, A, 1X, E15.6)') 'Permutational symmetry error:', err call error('ccsd::do_ccsd', 'Permutational symmetry of antisymmetrised integrals does not hold') @@ -158,6 +160,34 @@ subroutine do_ccsd_spinorb(sys, int_store) write(iunit, *) t0=t1 + write(iunit, '(1X, A)') 'Forming slices of antisymmetrised spinorbital ERIs' + + ! We store only the slices needed: note that since we're moving to restricted indices, + ! the virtuals are 1:2*nvirt instead of 2*nocc+1:2*nbasis + ! All 4 occupied + allocate(cc_int%oooo, source=asym(1:2*nocc,1:2*nocc,1:2*nocc,1:2*nocc)) + ! 3 occupied, 1 virtual, of which there are 3 types: ovoo, oovo, ooov, which are all related by permutational sym + allocate(cc_int%ooov, source=asym(1:2*nocc,1:2*nocc,1:2*nocc,2*nocc+1:2*nbasis)) + !cc_int%ovoo = reshape(cc_int%ooov, (/2*nocc,2*nvirt,2*nocc,2*nocc/), order=(/1,4,3,2/)) + cc_int%oovo = -reshape(cc_int%ooov, (/2*nocc,2*nocc,2*nvirt,2*nocc/), order=(/1,2,4,3/)) + ! 2o2v + allocate(cc_int%oovv, source=asym(1:2*nocc,1:2*nocc,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis)) + cc_int%ovvo = -reshape(cc_int%oovv, (/2*nocc,2*nvirt,2*nvirt,2*nocc/), order=(/1,4,3,2/)) + ! 1o3v + allocate(cc_int%ovvv, source=asym(1:2*nocc,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis)) + !cc_int%vovv = -reshape(cc_int%ovvv, (/2*nvirt,2*nocc,2*nvirt,2*nvirt/), order=(/2,1,3,4/)) + ! 4v + allocate(cc_int%vvvv, source=asym(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis)) + + call system_clock(t1) + if (t1sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, nvirt=>sys%nvirt, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab,& W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau, W_vvvv=>cc_int%W_vvvv) W_oooo = 0.0_p W_ovvo = 0.0_p - !$omp parallel default(none) & - !$omp private(m, n, i, j, e, f, b, x, a) & - !$omp shared(sys, cc_int, cc_amp, asym) - + ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed ! by a simple dgemm call - !$omp do schedule(static, 10) collapse(4) - do n = 1, 2*nocc - do m = 1, 2*nocc - do j = 1, 2*nocc - do i = 1, 2*nocc - W_oooo(i,j,m,n) = asym(i,j,m,n) - do e = 2*nocc+1, 2*nbasis - W_oooo(i,j,m,n) = W_oooo(i,j,m,n) + t_ia(j,e)*asym(e,i,n,m) - t_ia(i,e)*asym(e,j,n,m) - do f = 2*nocc+1, 2*nbasis - W_oooo(i,j,m,n) = W_oooo(i,j,m,n) - 0.5*t_ijab(j,i,f,e)*asym(f,e,m,n) - end do - end do - end do - end do - end do - end do - !$omp end do + allocate(scratch, mold=W_oooo) - ! [TODO]: make a switch to on-the-fly W_vvvv computation, for when memory is limited - ! Similarly, we order it (e,f,a,b) for the contraction tau_ij^ef W_abef - !$omp do schedule(static, 10) collapse(4) - do b = 2*nocc+1, 2*nbasis - do a = 2*nocc+1, 2*nbasis - do f = 2*nocc+1, 2*nbasis - do e = 2*nocc+1, 2*nbasis - W_vvvv(e,f,a,b) = asym(e,f,a,b) - do n = 1, 2*nocc - W_vvvv(e,f,a,b) = W_vvvv(e,f,a,b) + t_ia(n,b)*asym(n,a,e,f) - t_ia(n,a)*asym(n,b,e,f) - end do - end do - end do - end do - end do - !$omp end do + call dgemm('N','T',8*nocc**3,2*nocc,2*nvirt,cc_int%ooov,t1,scratch) + W_oooo = cc_int%oooo + scratch + + reshape_scratch = reshape(scratch, (/2*nocc,2*nocc,2*nocc,2*nocc/), order=(/1,2,4,3/)) + W_oooo = W_oooo - reshape_scratch + + reshape_scratch = reshape(tau, (/2*nvirt,2*nvirt,2*nocc,2*nocc/), order=(/3,4,1,2/)) + call dgemm('N','N',4*nocc**2,4**nocc**2,4*nvirt**2,cc_int%oovv,reshape_scratch,scratch) + W_oooo = W_oooo + scratch/2 + + reshape_scratch = reshape(W_oooo, (/2*nocc,2*nocc,2*nocc,2*nocc/), order=(/3,4,1,2/)) + W_oooo = reshape_scratch + + deallocate(scratch) + allocate(scratch, mold=W_vvvv) + + ! - P_(ab) t_m^b = + P_(ab) (t_b^m)^T , plus another sign change, which is most easily explained + ! if we look at it by element: t_b^m = \sum_m t_b^m = -\sum_m t_b^m + call dgemm_wrapper('T','N',2*nvirt,8*nvirt**3,2*nocc,t1,cc_int%ovvv,scratch) + W_vvvv = cc_int%vvvv - scratch + reshape_scratch = reshape(scratch,(/2*nvirt,2*nvirt,2*nvirt,2*nvirt/),order=(/2,1,3,4/)) + W_vvvv = W_vvvv + scratch + deallocate(scratch) + allocate(scratch, mold=W_ovvo) + + call dgemm_wrapper('N','T',8*nocc*nvirt**2,2*nocc,2*nvirt,cc_int%ovvo,t1,scratch) + W_ovvo = cc_int%ovvo + scratch + call dgemm_wrapper('T','N',2*nvirt,8*nocc**2*nvirt,2*nocc,t1,cc_int%oovo,scratch) + W_ovvo = W_ovvo - scratch + + !$omp parallel default(none) & + !$omp private(x) & + !$omp shared(cc_amp,asym) !$omp do schedule(static, 10) collapse(4) do j = 1, 2*nocc do e = 2*nocc+1, 2*nbasis do b = 2*nocc+1, 2*nbasis do m = 1, 2*nocc - W_ovvo(m,b,e,j) = asym(m,b,e,j) - do f = 2*nocc+1, 2*nbasis - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - t_ia(j,f)*asym(f,e,m,b) - end do - do n = 1, 2*nocc - x = t_ia(n,b) - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) + x*asym(n,m,e,j) + x = t1(n,b) do f = 2*nocc+1, 2*nbasis - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t_ijab(j,n,f,b) + x*t_ia(j,f)) * asym(f,e,n,m) + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + x*t1(j,f)) * asym(f,e,n,m) end do end do end do From 9ed5a43cf3c487567e3435583a18dfe9a39a3f72 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Tue, 25 Jan 2022 13:33:54 +0000 Subject: [PATCH 51/71] Syncing commit, to see if a segfault is caused by limited memory --- src/ccsd.f90 | 17 ++++++++++++----- 1 file changed, 12 insertions(+), 5 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 87356af..a5257ee 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -759,22 +759,28 @@ subroutine build_W(sys, cc_int, cc_amp, asym) ! by a simple dgemm call allocate(scratch, mold=W_oooo) - call dgemm('N','T',8*nocc**3,2*nocc,2*nvirt,cc_int%ooov,t1,scratch) + ! Eq. 6: W_mnij = + P_(ij) \sum_e t_j^e + 1/2\sum_{ef} tau_ij^ef + ! This performs the identity in the perm. operator + call dgemm_wrapper('N','T',8*nocc**3,2*nocc,2*nvirt,cc_int%ooov,t1,scratch) + ! This adds to W_mnij W_oooo = cc_int%oooo + scratch - + ! This performs the i<->j swap in the perm. operator reshape_scratch = reshape(scratch, (/2*nocc,2*nocc,2*nocc,2*nocc/), order=(/1,2,4,3/)) W_oooo = W_oooo - reshape_scratch - + ! This performs the last contraction reshape_scratch = reshape(tau, (/2*nvirt,2*nvirt,2*nocc,2*nocc/), order=(/3,4,1,2/)) - call dgemm('N','N',4*nocc**2,4**nocc**2,4*nvirt**2,cc_int%oovv,reshape_scratch,scratch) + print*, '1' + call dgemm_wrapper('N','N',4*nocc**2,4**nocc**2,4*nvirt**2,cc_int%oovv,reshape_scratch,scratch) + print*, '2' W_oooo = W_oooo + scratch/2 - + print*, '3' reshape_scratch = reshape(W_oooo, (/2*nocc,2*nocc,2*nocc,2*nocc/), order=(/3,4,1,2/)) W_oooo = reshape_scratch deallocate(scratch) allocate(scratch, mold=W_vvvv) + ! - P_(ab) t_m^b = + P_(ab) (t_b^m)^T , plus another sign change, which is most easily explained ! if we look at it by element: t_b^m = \sum_m t_b^m = -\sum_m t_b^m call dgemm_wrapper('T','N',2*nvirt,8*nvirt**3,2*nocc,t1,cc_int%ovvv,scratch) @@ -785,6 +791,7 @@ subroutine build_W(sys, cc_int, cc_amp, asym) deallocate(scratch) allocate(scratch, mold=W_ovvo) + print*, '2' call dgemm_wrapper('N','T',8*nocc*nvirt**2,2*nocc,2*nvirt,cc_int%ovvo,t1,scratch) W_ovvo = cc_int%ovvo + scratch call dgemm_wrapper('T','N',2*nvirt,8*nocc**2*nvirt,2*nocc,t1,cc_int%oovo,scratch) From 0c4a086c57dd44e7e1eb57c8cad0876e264ae52a Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Tue, 25 Jan 2022 13:39:30 +0000 Subject: [PATCH 52/71] Add data --- dat/els.in | 7 + dat/enuc.dat | 1 + dat/eri.dat | 29962 ++++++++++++++++++++++++++++++++++++++++++++++++ dat/geom.dat | 4 + dat/input.dat | 13 + dat/mux.dat | 351 + dat/muy.dat | 351 + dat/muz.dat | 351 + dat/s.dat | 351 + dat/t.dat | 351 + dat/v.dat | 351 + 11 files changed, 32093 insertions(+) create mode 100644 dat/els.in create mode 100644 dat/enuc.dat create mode 100644 dat/eri.dat create mode 100644 dat/geom.dat create mode 100644 dat/input.dat create mode 100644 dat/mux.dat create mode 100644 dat/muy.dat create mode 100644 dat/muz.dat create mode 100644 dat/s.dat create mode 100644 dat/t.dat create mode 100644 dat/v.dat diff --git a/dat/els.in b/dat/els.in new file mode 100644 index 0000000..bc0e85e --- /dev/null +++ b/dat/els.in @@ -0,0 +1,7 @@ +&elsinput +calc_type="CCSD(T)_spinorb", +scf_e_tol=1e-7, +scf_d_tol=1e-6, +ccsd_e_tol=1e-7, +ccsd_t_tol=1e-6 +/ diff --git a/dat/enuc.dat b/dat/enuc.dat new file mode 100644 index 0000000..6b08fe4 --- /dev/null +++ b/dat/enuc.dat @@ -0,0 +1 @@ + 8.002367061810450 diff --git a/dat/eri.dat b/dat/eri.dat new file mode 100644 index 0000000..dde2d26 --- /dev/null +++ b/dat/eri.dat @@ -0,0 +1,29962 @@ + 1 1 1 1 6.354189973248753 + 2 1 1 1 4.387899442371338 + 2 2 1 1 4.238794327695956 + 2 1 2 1 3.193013316302158 + 2 2 2 1 3.248124693774366 + 2 2 2 2 3.483787305264849 + 3 1 1 1 1.241927819887143 + 3 2 1 1 1.437384455806511 + 3 1 2 1 0.942508225976321 + 3 2 2 1 1.137866105265517 + 3 1 2 2 1.006882123422589 + 3 2 2 2 1.267869777508532 + 3 3 1 1 1.515598235070410 + 3 1 3 1 0.297919761155189 + 3 3 2 1 1.255112295756863 + 3 2 3 1 0.372597901093569 + 3 3 2 2 1.475942823468732 + 3 2 3 2 0.482279547253520 + 3 3 3 1 0.472289079534761 + 3 3 3 2 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-0.000000000000000 + 24 14 -2.587720019657160 + 24 15 0.000000000000001 + 24 16 -1.261764223414275 + 24 17 -0.379419250015790 + 24 18 -1.180615746113683 + 24 19 0.933886002825542 + 24 20 0.117480030424316 + 24 21 0.000000000000000 + 24 22 -0.837259808785775 + 24 23 -0.968086093462564 + 24 24 -5.337318088575110 + 25 1 1.041532041426785 + 25 2 1.087226336943882 + 25 3 2.089966098086458 + 25 4 1.813243282076082 + 25 5 -2.150961121302793 + 25 6 0.580563626208157 + 25 7 -0.000000000000001 + 25 8 -1.431232206102101 + 25 9 -0.419763257884820 + 25 10 -0.000000000000000 + 25 11 2.618759658432143 + 25 12 -0.394236942305063 + 25 13 0.000000000000001 + 25 14 0.581373626195615 + 25 15 -0.000000000000000 + 25 16 0.977558092898016 + 25 17 0.045875370757841 + 25 18 0.271210253055883 + 25 19 -0.117480030424315 + 25 20 -0.148274896118442 + 25 21 -0.000000000000000 + 25 22 0.614631984366797 + 25 23 0.708919083259977 + 25 24 0.421852120753141 + 25 25 -5.098518532178510 + 26 1 -0.000000000000000 + 26 2 -0.000000000000000 + 26 3 -0.000000000000001 + 26 4 -0.000000000000001 + 26 5 0.000000000000001 + 26 6 -0.000000000000001 + 26 7 -1.115421164671683 + 26 8 0.000000000000001 + 26 9 -0.000000000000000 + 26 10 -1.545237512116846 + 26 11 -0.000000000000001 + 26 12 0.000000000000001 + 26 13 0.896066315375577 + 26 14 -0.000000000000001 + 26 15 -0.708323891495739 + 26 16 0.000000000000000 + 26 17 -0.000000000000000 + 26 18 -0.000000000000000 + 26 19 0.000000000000000 + 26 20 0.000000000000000 + 26 21 -0.109166181788804 + 26 22 -0.000000000000000 + 26 23 -0.000000000000000 + 26 24 -0.000000000000000 + 26 25 0.000000000000000 + 26 26 -4.768931533722705 From d7d93d353273487969610c528031f6a148f403d3 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Tue, 25 Jan 2022 18:31:56 +0000 Subject: [PATCH 53/71] Reshape_scratch sync commit --- src/ccsd.f90 | 321 +++++++++++++++++++++++------------------------ src/geometry.f90 | 11 +- src/main.F90 | 3 +- src/system.f90 | 11 +- 4 files changed, 179 insertions(+), 167 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index a5257ee..21b3f63 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -163,21 +163,23 @@ subroutine do_ccsd_spinorb(sys, int_store) write(iunit, '(1X, A)') 'Forming slices of antisymmetrised spinorbital ERIs' ! We store only the slices needed: note that since we're moving to restricted indices, - ! the virtuals are 1:2*nvirt instead of 2*nocc+1:2*nbasis + ! the virtuals are 1:nvirt instead of nocc+1:nbasis. Also in system.f90 we take care of the factor of 2 + ! between restricted/unrestricted bounds + ! All 4 occupied - allocate(cc_int%oooo, source=asym(1:2*nocc,1:2*nocc,1:2*nocc,1:2*nocc)) + allocate(cc_int%oooo, source=asym(1:nocc,1:nocc,1:nocc,1:nocc)) ! 3 occupied, 1 virtual, of which there are 3 types: ovoo, oovo, ooov, which are all related by permutational sym - allocate(cc_int%ooov, source=asym(1:2*nocc,1:2*nocc,1:2*nocc,2*nocc+1:2*nbasis)) - !cc_int%ovoo = reshape(cc_int%ooov, (/2*nocc,2*nvirt,2*nocc,2*nocc/), order=(/1,4,3,2/)) - cc_int%oovo = -reshape(cc_int%ooov, (/2*nocc,2*nocc,2*nvirt,2*nocc/), order=(/1,2,4,3/)) + allocate(cc_int%ooov, source=asym(1:nocc,1:nocc,1:nocc,nocc+1:2*nbasis)) + cc_int%ovoo = reshape(cc_int%ooov, (/nocc,nvirt,nocc,nocc/), order=(/1,4,3,2/)) + cc_int%oovo = -reshape(cc_int%ooov, (/nocc,nocc,nvirt,nocc/), order=(/1,2,4,3/)) ! 2o2v - allocate(cc_int%oovv, source=asym(1:2*nocc,1:2*nocc,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis)) - cc_int%ovvo = -reshape(cc_int%oovv, (/2*nocc,2*nvirt,2*nvirt,2*nocc/), order=(/1,4,3,2/)) + allocate(cc_int%oovv, source=asym(1:nocc,1:nocc,nocc+1:2*nbasis,nocc+1:2*nbasis)) + cc_int%ovvo = -reshape(cc_int%oovv, (/nocc,nvirt,nvirt,nocc/), order=(/1,4,3,2/)) ! 1o3v - allocate(cc_int%ovvv, source=asym(1:2*nocc,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis)) - !cc_int%vovv = -reshape(cc_int%ovvv, (/2*nvirt,2*nocc,2*nvirt,2*nvirt/), order=(/2,1,3,4/)) + allocate(cc_int%ovvv, source=asym(1:nocc,nocc+1:2*nbasis,nocc+1:2*nbasis,nocc+1:2*nbasis)) + cc_int%vovv = -reshape(cc_int%ovvv, (/nvirt,nocc,nvirt,nvirt/), order=(/2,1,3,4/)) ! 4v - allocate(cc_int%vvvv, source=asym(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis)) + allocate(cc_int%vvvv, source=asym(nocc+1:2*nbasis,nocc+1:2*nbasis,nocc+1:2*nbasis,nocc+1:2*nbasis)) call system_clock(t1) if (t1sys%nbasis, nocc=>sys%nocc, e=>sys%canon_levels) - allocate(cc_int%D_ia(2*nocc, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%D_ia', 4*nocc*(n-nocc), ierr) - allocate(cc_int%D_ijab(2*nocc, 2*nocc, 2*nocc+1:2*n, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%D_ijab', 16*(nocc**2*(n-nocc)**2), ierr) - do i = 1, nocc - do a = nocc+1, n - cc_int%D_ia(2*i-1:2*i,2*a-1:2*a) = e(i)-e(a) - do j = 1, nocc - do b = nocc+1, n - cc_int%D_ijab(2*i-1:2*i, 2*j-1:2*j, 2*a-1:2*a, 2*b-1:2*b) = e(i)+e(j)-e(a)-e(b) + ! Note that abcd...ijkl... etc are **restricted** indices, so the lower bounds can be set to one, i.e. default Fortran + associate(nvirt=>sys%nvirt, nocc=>sys%nocc, e=>sys%canon_levels) + allocate(cc_int%D_ia(nocc, nvirt), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%D_ia', nocc*nvirt, ierr) + allocate(cc_int%D_ijab(nocc, nocc, nvirt, nvirt), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%D_ijab', nocc**2*nvirt**2, ierr) + do i = 1, nocc/2 + do a = 1, nvirt/2 + cc_int%D_ia(2*i-1:2*i,2*a-1:2*a) = e(i)-e(a+nocc/2) + do j = 1, nocc/2 + do b = 1, nvirt/2 + cc_int%D_ijab(2*i-1:2*i, 2*j-1:2*j, 2*a-1:2*a, 2*b-1:2*b) = e(i)+e(j)-e(a+nocc/2)-e(b+nocc/2) end do end do end do end do ! This is only later useful in CCSD(T) but we can just do it here... - allocate(sys%canon_levels_spinorb(2*n), source=0.0_dp) - do i = 1, n + allocate(sys%canon_levels_spinorb(2*sys%nbasis), source=0.0_dp) + do i = 1, sys%nbasis sys%canon_levels_spinorb(2*i-1:2*i) = e(i) end do write(iunit, '(1X, A)') 'Allocating amplitude tensors...' ! Initialise t_i^a=0 and t_{ij}^{ab}=MP1 WF - allocate(cc_amp%t_ijab(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('cc_amp%t_ijab', 16*(nocc**2*(n-nocc)**2), ierr) + allocate(cc_amp%t_ijab(nocc,nocc,nvirt,nvirt), source=0.0_dp, stat=ierr) + call check_allocate('cc_amp%t_ijab', (nocc*nvirt)**2, ierr) allocate(cc_int%tmp_tijab, mold=cc_amp%t_ijab, stat=ierr) - call check_allocate('cc_int%tmp_tijab', 16*(nocc**2*(n-nocc)**2), ierr) - allocate(cc_amp%t_ia(2*nocc, 2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('cc_amp%t_ia', 4*nocc*(n-nocc), ierr) + call check_allocate('cc_int%tmp_tijab', (nocc*nvirt)**2, ierr) + allocate(cc_amp%t_ia(nocc, nvirt), source=0.0_dp, stat=ierr) + call check_allocate('cc_amp%t_ia', nocc*nvirt, ierr) allocate(cc_int%tmp_tia, mold=cc_amp%t_ia, stat=ierr) - call check_allocate('cc_int%tmp_tia', 4*nocc*(n-nocc), ierr) - end associate + call check_allocate('cc_int%tmp_tia', nocc*nvirt, ierr) write(iunit, '(1X, A)') 'Forming initial amplitude guesses...' - associate(doubles=>cc_amp%t_ijab, nocc=>sys%nocc, asym=>int_store%asym_spinorb) - do p = 1, 2*nocc - do q = 1, 2*nocc - do r = 2*sys%nocc+1, 2*sys%nbasis - do s = 2*sys%nocc+1, 2*sys%nbasis - doubles(p,q,r,s) = asym(p,q,r,s)/cc_int%D_ijab(p,q,r,s) - end do - end do - end do - end do - end associate + cc_amp%t_ijab = cc_int%oovv / cc_int%D_ijab - write(iunit, '(1X, A)') 'Allocating intermediate tensors...' + write(iunit, '(1X, A)') 'Allocating stored intermediate tensors...' ! Allocate the intermediate tensors - associate(n=>sys%nbasis, nocc=>sys%nocc) - allocate(cc_int%F_vv(2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%F_vv', 4*(n-nocc)**2, ierr) - allocate(cc_int%F_oo(2*nocc,2*nocc), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%F_oo', 4*nocc**2, ierr) - allocate(cc_int%F_ov(2*nocc,2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%F_ov', 4*nocc*(n-nocc), ierr) - allocate(cc_int%W_oooo(2*nocc,2*nocc,2*nocc,2*nocc), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%W_oooo', 16*nocc**4, ierr) - allocate(cc_int%W_vvvv(2*nocc+1:2*n,2*nocc+1:2*n,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%W_vvvv', 16*(n-nocc)**4, ierr) - allocate(cc_int%W_ovvo(2*nocc,2*nocc+1:2*n,2*nocc+1:2*n,2*nocc), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%W_ovvo', 16*nocc**2*(n-nocc)**2, ierr) - allocate(cc_int%tau(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%tau', 16*nocc**2*(n-nocc)**2, ierr) - allocate(cc_int%tau_tilde(2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_dp, stat=ierr) - call check_allocate('cc_int%tau_tilde', 16*nocc**2*(n-nocc)**2, ierr) + allocate(cc_int%F_vv(nvirt,nvirt), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%F_vv', nvirt**2, ierr) + allocate(cc_int%F_oo(nocc,nocc), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%F_oo', nocc**2, ierr) + allocate(cc_int%F_ov(nocc,nvirt), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%F_ov', nocc*nvirt, ierr) + allocate(cc_int%W_oooo(nocc,nocc,nocc,nocc), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%W_oooo', nocc**4, ierr) + allocate(cc_int%W_vvvv(nvirt,nvirt,nvirt,nvirt), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%W_vvvv', nvirt**4, ierr) + allocate(cc_int%W_ovvo(nocc,nvirt,nvirt,nocc), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%W_ovvo', (nocc*nvirt)**2, ierr) + allocate(cc_int%tau(nocc,nocc,nvirt,nvirt), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%tau', (nocc*nvirt)**2, ierr) + allocate(cc_int%tau_tilde(nocc,nocc,nvirt,nvirt), source=0.0_dp, stat=ierr) + call check_allocate('cc_int%tau_tilde', (nocc*nvirt)**2, ierr) end associate end subroutine init_cc @@ -527,11 +519,11 @@ subroutine init_diis_cc_t(sys, diis) allocate(diis%idx(diis%n_errmat,2), source=0) - associate(n=>sys%nbasis, nocc=>sys%nocc) - allocate(diis%t1(diis%n_errmat,2*nocc,2*nocc+1:2*n), source=0.0_p, stat=ierr) - call check_allocate('diis%t1', diis%n_errmat*4*nocc*(n-nocc), ierr) - allocate(diis%t2(diis%n_errmat,2*nocc,2*nocc,2*nocc+1:2*n,2*nocc+1:2*n), source=0.0_p, stat=ierr) - call check_allocate('diis%t1', diis%n_errmat*16*(nocc*(n-nocc))**2, ierr) + associate(nvirt=>sys%nvirt, nocc=>sys%nocc) + allocate(diis%t1(diis%n_errmat,nocc,nvirt), source=0.0_p, stat=ierr) + call check_allocate('diis%t1', diis%n_errmat*nocc*nvirt, ierr) + allocate(diis%t2(diis%n_errmat,nocc,nocc,nvirt,nvirt), source=0.0_p, stat=ierr) + call check_allocate('diis%t1', diis%n_errmat*(nocc*nvirt)**2, ierr) end associate end subroutine init_diis_cc_t @@ -627,7 +619,7 @@ subroutine build_tau(sys, cc_amp, cc_int) integer :: i, j, a, b real(p) :: ia, ja, x - associate(n=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& + associate(nvirt=>sys%nvirt, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& tau=>cc_int%tau, tau_tilde=>cc_int%tau_tilde) tau = 0.0_p tau_tilde = 0.0_p @@ -635,11 +627,11 @@ subroutine build_tau(sys, cc_amp, cc_int) !$omp private(i,j,a,b,ia,ja,x) & !$omp shared(sys, cc_amp, cc_int) & !$omp schedule(static, 10) collapse(2) - do b = 2*nocc+1, 2*n - do a = 2*nocc+1, 2*n - do j = 1, 2*nocc + do b = 1, nvirt + do a = 1, nvirt + do j = 1, nocc ja = t_ia(j,a) - do i = 1, 2*nocc + do i = 1, nocc x = t_ia(i,a)*t_ia(j,b) - t_ia(i,b)*ja tau_tilde(i,j,a,b) = t_ijab(i,j,a,b) + 0.5*x tau(i,j,a,b) = tau_tilde(i,j,a,b) + 0.5*x @@ -669,7 +661,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) integer :: a, e, f, m, n, i - associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& + associate(nvirt=>sys%nvirt, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& F_vv=>cc_int%F_vv, F_oo=>cc_int%F_oo, F_ov=>cc_int%F_ov, tau_tilde=>cc_int%tau_tilde) F_vv = 0.0_p @@ -682,13 +674,13 @@ subroutine build_F(sys, cc_int, cc_amp, asym) ! F_ae = \sum_{mf} t_m^f * - 0.5 \sum_{mnf} \tau~_{mn}^{af} !$omp do schedule(static, 10) collapse(2) - do a = 2*nocc+1, 2*nbasis - do e = 2*nocc+1, 2*nbasis - do m = 1, 2*nocc - do f = 2*nocc+1, 2*nbasis - F_vv(a,e) = F_vv(a,e) + t_ia(m,f) * asym(f,e,m,a) - do n = 1, 2*nocc - F_vv(a,e) = F_vv(a,e) + 0.5*tau_tilde(n,m,f,a)*asym(n,m,e,f) + do a = 1, nvirt + do e = 1, nvirt + do m = 1, nocc + do f = 1, nvirt + F_vv(a,e) = F_vv(a,e) + t_ia(m,f) * cc_int%ovvv(m,a,f,e) + do n = 1, nocc + F_vv(a,e) = F_vv(a,e) + 0.5*tau_tilde(n,m,f,a)*cc_int%oovv(n,m,e,f) end do end do end do @@ -698,14 +690,13 @@ subroutine build_F(sys, cc_int, cc_amp, asym) ! F_mi = \sum_{en} t_n^e + 0.5 \sum_{nef} \tau~_{in}^{ef} !$omp do schedule(static, 10) collapse(2) - do m = 1, 2*nocc - do i = 1, 2*nocc - do e = 2*nocc+1, 2*nbasis - do n = 1, 2*nocc - F_oo(m,i) = F_oo(m,i) - t_ia(n,e)*asym(n,m,i,e) - do f = 2*nocc+1, 2*nbasis - F_oo(m,i) = F_oo(m,i) - 0.5*tau_tilde(n,i,f,e)*asym(f,e,m,n) - end do + do m = 1, nocc + do i = 1, nocc + do e = 1, nvirt + do n = 1, nocc + F_oo(m,i) = F_oo(m,i) - t_ia(n,e)*cc_int%ooov(n,m,i,e) + ! [todo] - This is terrible cache-wise, but does it warrant creating a new slice/doing a reshape? + F_oo(m,i) = F_oo(m,i) - 0.5*dot_product(tau_tilde(n,i,:,e),cc_int%oovv(m,n,e,:)) end do end do end do @@ -714,13 +705,10 @@ subroutine build_F(sys, cc_int, cc_amp, asym) ! F_me = \sum_{nf} t_n^f * !$omp do schedule(static, 10) collapse(2) - do m = 1, 2*nocc - do e = 2*nocc+1, 2*nbasis - do n = 1, 2*nocc - do f = 2*nocc+1, 2*nbasis - F_ov(m,e) = F_ov(m,e) + t_ia(n,f)*asym(f,e,n,m) - end do - end do + do m = 1, nocc + do e = 1, nvirt + ! [todo] - same as above, also investigate if sum(A*B) is better in cases of missed cache + F_ov(m,e) = F_ov(m,e) + sum(t_ia(:,:)*cc_int%oovv(m,:,e,:)) end do end do !$omp end do @@ -761,54 +749,61 @@ subroutine build_W(sys, cc_int, cc_amp, asym) ! Eq. 6: W_mnij = + P_(ij) \sum_e t_j^e + 1/2\sum_{ef} tau_ij^ef ! This performs the identity in the perm. operator - call dgemm_wrapper('N','T',8*nocc**3,2*nocc,2*nvirt,cc_int%ooov,t1,scratch) + print*,'dgemm' + call dgemm_wrapper('N','T',nocc**3,nocc,nocc,cc_int%ooov,t1,scratch) ! This adds to W_mnij W_oooo = cc_int%oooo + scratch ! This performs the i<->j swap in the perm. operator - reshape_scratch = reshape(scratch, (/2*nocc,2*nocc,2*nocc,2*nocc/), order=(/1,2,4,3/)) - W_oooo = W_oooo - reshape_scratch +! reshape_scratch = reshape(scratch, (/nocc,nocc,nocc,nocc/), order=(/1,2,4,3/)) +! W_oooo = W_oooo - reshape_scratch + W_oooo = W_oooo - reshape(scratch, (/nocc,nocc,nocc,nocc/), order=(/1,2,4,3/)) ! This performs the last contraction - reshape_scratch = reshape(tau, (/2*nvirt,2*nvirt,2*nocc,2*nocc/), order=(/3,4,1,2/)) - print*, '1' - call dgemm_wrapper('N','N',4*nocc**2,4**nocc**2,4*nvirt**2,cc_int%oovv,reshape_scratch,scratch) - print*, '2' +! reshape_scratch = reshape(tau, (/nvirt,nvirt,nocc,nocc/), order=(/3,4,1,2/)) + print*,'dgemm' + call dgemm_wrapper('N','N',nocc**2,nocc**2,nvirt**2,cc_int%oovv,& + reshape(tau, (/nvirt,nvirt,nocc,nocc/), order=(/3,4,1,2/)),scratch) W_oooo = W_oooo + scratch/2 - print*, '3' - reshape_scratch = reshape(W_oooo, (/2*nocc,2*nocc,2*nocc,2*nocc/), order=(/3,4,1,2/)) - W_oooo = reshape_scratch +! reshape_scratch = reshape(W_oooo, (/nocc,nocc,nocc,nocc/), order=(/3,4,1,2/)) + W_oooo = reshape(W_oooo, (/nocc,nocc,nocc,nocc/), order=(/3,4,1,2/)) deallocate(scratch) allocate(scratch, mold=W_vvvv) - ! - P_(ab) t_m^b = + P_(ab) (t_b^m)^T , plus another sign change, which is most easily explained ! if we look at it by element: t_b^m = \sum_m t_b^m = -\sum_m t_b^m - call dgemm_wrapper('T','N',2*nvirt,8*nvirt**3,2*nocc,t1,cc_int%ovvv,scratch) + print*,'dgemm' + call dgemm_wrapper('T','N',nocc,nvirt**3,nocc,t1,cc_int%ovvv,scratch) W_vvvv = cc_int%vvvv - scratch - reshape_scratch = reshape(scratch,(/2*nvirt,2*nvirt,2*nvirt,2*nvirt/),order=(/2,1,3,4/)) - W_vvvv = W_vvvv + scratch +! reshape_scratch = reshape(scratch,(/nvirt,nvirt,nvirt,nvirt/),order=(/2,1,3,4/)) +! W_vvvv = W_vvvv + reshape_scratch + W_vvvv = W_vvvv + reshape(scratch,(/nvirt,nvirt,nvirt,nvirt/),order=(/2,1,3,4/)) +! reshape_scratch = reshape(W_vvvv,(/nvirt,nvirt,nvirt,nvirt/),order=(/3,4,1,2/)) +! W_vvvv = reshape_scratch + W_vvvv = reshape(W_vvvv,(/nvirt,nvirt,nvirt,nvirt/),order=(/3,4,1,2/)) deallocate(scratch) allocate(scratch, mold=W_ovvo) - print*, '2' - call dgemm_wrapper('N','T',8*nocc*nvirt**2,2*nocc,2*nvirt,cc_int%ovvo,t1,scratch) + print*,'dgemm' + call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nocc,cc_int%ovvo,t1,scratch) W_ovvo = cc_int%ovvo + scratch - call dgemm_wrapper('T','N',2*nvirt,8*nocc**2*nvirt,2*nocc,t1,cc_int%oovo,scratch) + print*,'dgemm' + call dgemm_wrapper('T','N',nocc,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) W_ovvo = W_ovvo - scratch !$omp parallel default(none) & !$omp private(x) & - !$omp shared(cc_amp,asym) + !$omp shared(cc_amp,asym,cc_int) !$omp do schedule(static, 10) collapse(4) - do j = 1, 2*nocc - do e = 2*nocc+1, 2*nbasis - do b = 2*nocc+1, 2*nbasis - do m = 1, 2*nocc - do n = 1, 2*nocc + do j = 1, nocc + do e = 1, nvirt + do b = 1, nvirt + do m = 1, nocc + do n = 1, nocc x = t1(n,b) - do f = 2*nocc+1, 2*nbasis - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + x*t1(j,f)) * asym(f,e,n,m) + do f = 1, nvirt + ! [todo]: bad cache behaviour (last term), however dgemm isn't that much better herem since two reshapes needed. + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + x*t1(j,f)) * cc_int%oovv(m,n,e,f) end do end do end do @@ -844,7 +839,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) associate(tmp_t1=>cc_int%tmp_tia,tmp_t2=>cc_int%tmp_tijab,t1=>cc_amp%t_ia,t2=>cc_amp%t_ijab,asym=>int_store%asym_spinorb, & F_oo=>cc_int%F_oo,F_ov=>cc_int%F_ov,F_vv=>cc_int%F_vv,D_ia=>cc_int%D_ia,D_ijab=>cc_int%D_ijab,W_oooo=>cc_int%W_oooo, & - W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nbasis=>sys%nbasis,nvirt=>sys%nvirt,& + W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nvirt=>sys%nvirt,& W_vvvv=>cc_int%W_vvvv) ! Update T1 @@ -859,22 +854,22 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) ! tmp_t1 can be shared as each loop iteration will update a unique element of it. !$omp do schedule(static, 10) collapse(2) - do a = 2*nocc+1, 2*nbasis - do i = 1, 2*nocc - do m = 1, 2*nocc - do e = 2*nocc+1, 2*nbasis + do a = 1, nvirt + do i = 1, nocc + do m = 1, nocc + do e = 1, nvirt tmp_t1(i,a) = tmp_t1(i,a) + t2(m,i,e,a)*F_ov(m,e) - do f = 2*nocc+1, 2*nbasis - tmp_t1(i,a) = tmp_t1(i,a) + 0.5*t2(m,i,f,e)*asym(f,e,m,a) + do f = 1, nvirt + tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(m,i,f,e)*cc_int%ovvv(m,a,e,f) end do - do n = 1, 2*nocc - tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(n,m,e,a)*asym(n,m,e,i) + do n = 1, nocc + tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(n,m,e,a)*cc_int%oovo(n,m,e,i) end do end do end do - do e = 2*nocc+1, 2*nbasis - do n = 1, 2*nocc - tmp_t1(i,a) = tmp_t1(i,a) - t1(n,e)*asym(n,a,i,e) + do e = 1, nvirt + do n = 1, nocc + tmp_t1(i,a) = tmp_t1(i,a) - t1(n,e)*cc_int%oovv(n,i,a,e) end do end do end do @@ -885,38 +880,37 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) tmp_t1 = tmp_t1/D_ia ! Update T2 - + tmp_t2 = cc_int%oovv !$omp parallel default(none) & !$omp shared(sys, cc_amp, int_store, cc_int) !$omp do schedule(static, 10) collapse(4) - do b = 2*nocc+1, 2*nbasis - do a = 2*nocc+1, 2*nbasis - do j = 1, 2*nocc - do i = 1, 2*nocc - tmp_t2(i,j,a,b) = asym(i,j,a,b) - do e = 2*nocc+1, 2*nbasis + do b = 1, nvirt + do a = 1, nvirt + do j = 1, nocc + do i = 1, nocc + do e = 1, nvirt tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(j,i,e,b)*F_vv(a,e) & - + tmp_t1(i,e)*asym(e,j,a,b) - tmp_t1(j,e)*asym(e,i,a,b) - do m = 1, 2*nocc + + tmp_t1(i,e)*cc_int%vovv(e,j,a,b) - tmp_t1(j,e)*cc_int%vovv(e,i,a,b) + do m = 1, nocc tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*F_ov(m,e)*t2(i,j,b,e)*tmp_t1(m,a) end do end do - do m = 1, 2*nocc + do m = 1, nocc tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(m,i,b,a)*F_oo(m,j) + t2(m,j,b,a)*F_oo(m,i) & - - tmp_t1(m,a)*asym(m,b,i,j) + tmp_t1(m,b)*asym(m,a,i,j) - do e = 2*nocc+1, 2*nbasis + - tmp_t1(m,a)*cc_int%ovoo(m,b,i,j) + tmp_t1(m,b)*cc_int%ovoo(m,a,i,j) + do e = 1, nvirt tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*tmp_t1(j,e)-& t2(j,m,a,b)*tmp_t1(i,e)) end do end do - do m = 1, 2*nocc - do e = 2*nocc+1, 2*nbasis + do m = 1, nocc + do e = 1, nvirt tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & - + t2(m,i,e,a)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*asym(e,j,m,b)& - - t2(m,j,e,a)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*asym(e,i,m,b)& - - t2(m,i,e,b)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*asym(e,j,m,a)& - + t2(m,j,e,b)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*asym(e,i,m,a) + + t2(m,i,e,a)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*cc_int%oovv(m,j,e,b)& + - t2(m,j,e,a)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*cc_int%oovv(m,i,e,b)& + - t2(m,i,e,b)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*cc_int%oovv(m,j,e,a)& + + t2(m,j,e,b)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*cc_int%oovv(m,i,e,a) end do end do end do @@ -929,11 +923,14 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) allocate(tmp_t2_s, source=t2) ! t_ij^ae F_be - call dgemm_wrapper('N','T',8*nocc**2*nvirt,2*nvirt,2*nvirt,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) + print*,'dgemm' + call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s - call dgemm_wrapper('N','N',4*nocc**2,4*nvirt**2,4*nocc**2,W_oooo,tau,tmp_t2_s) + print*,'dgemm' + call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 - call dgemm_wrapper('N','N',4*nocc**2,4*nvirt**2,4*nvirt**2,tau,W_vvvv,tmp_t2_s) + print*,'dgemm' + call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 deallocate(tmp_t2_s) @@ -943,11 +940,11 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end subroutine update_amplitudes - subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) + subroutine update_cc_energy(sys, st, cc_int, cc_amp, conv) ! Updates the CC energy and also checks for convergence ! In: ! sys: system under study. - ! int_store: integral information. + ! cc_int: CC intermediates, of which we're using the cc_int%oovv slice. ! cc_amp: CC amplitudes. ! In/out: ! st: state_t object storing energies and RMS(T) info for convergence checking @@ -958,7 +955,7 @@ subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) use integrals, only: int_store_t type(system_t), intent(in) :: sys - type(int_store_t), intent(in) :: int_store + type(cc_int_t), intent(in) :: cc_int type(cc_amp_t), intent(in) :: cc_amp type(state_t), intent(inout) :: st logical, intent(out) :: conv @@ -968,18 +965,18 @@ subroutine update_cc_energy(sys, st, int_store, cc_amp, conv) conv = .false. st%energy_old = st%energy - associate(nocc=>sys%nocc, nbasis=>sys%nbasis, asym=>int_store%asym_spinorb, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab) + associate(nocc=>sys%nocc, nvirt=>sys%nvirt, oovv=>cc_int%oovv, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab) !$omp parallel default(none) & !$omp private(i,j,a,b) & - !$omp shared(sys,st,int_store,cc_amp,ecc,rmst2) + !$omp shared(sys,st,cc_amp,ecc,rmst2,cc_int) ecc = 0.0_p rmst2 = 0.0_p !$omp do schedule(static, 10) collapse(4) reduction(+:ecc,rmst2) - do b = 2*nocc+1, 2*nbasis - do a = 2*nocc+1, 2*nbasis - do j = 1, 2*nocc - do i = 1, 2*nocc - ecc = ecc + 0.25*asym(i,j,a,b)*(t2(i,j,a,b)+2*t1(i,a)*t1(j,b)) + do b = 1, nvirt + do a = 1, nvirt + do j = 1, nocc + do i = 1, nocc + ecc = ecc + 0.25*oovv(i,j,a,b)*(t2(i,j,a,b)+2*t1(i,a)*t1(j,b)) ! We only do the RMS on T2 amplitudes rmst2 = rmst2 + (t2(i,j,a,b)-st%t2_old(i,j,a,b))**2 end do diff --git a/src/geometry.f90 b/src/geometry.f90 index 96c5da7..51ac445 100644 --- a/src/geometry.f90 +++ b/src/geometry.f90 @@ -36,12 +36,17 @@ subroutine read_geometry_in(sys, int_store) close(ir) sys%nel = sum(sys%charges) - sys%nocc = sys%nel/2 - sys%nvirt = sys%nbasis - sys%nocc + + if (sys%restricted) then + sys%nocc = sys%nel/2 + sys%nvirt = sys%nbasis - sys%nocc + else + sys%nocc = sys%nel + sys%nvirt = (sys%nbasis - sys%nocc/2)*2 + end if call get_e_nuc(sys, int_store%e_nuc) - end subroutine read_geometry_in subroutine get_bond_lengths(sys, bondlengths) diff --git a/src/main.F90 b/src/main.F90 index e0265f9..8a74818 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -51,7 +51,8 @@ program main write(iunit, '(1X, A, 1X, F7.4, A)') 'Time taken for restricted Hartree-Fock:', real(t1-t0)/count_rate, "s" t0=t1 - call do_mp2_spinorb(sys, int_store) + ! Spinorbital MP2 is not currently implemented + call do_mp2_spatial(sys, int_store) call system_clock(t1) if (t1 Date: Tue, 25 Jan 2022 21:26:09 +0000 Subject: [PATCH 54/71] Fix misunderstanding in dgemm_wrapper concerning tranpose behaviour --- src/ccsd.f90 | 59 ++++++++++++++++++++++++-------------------------- src/linalg.f90 | 17 +++++++++++++-- 2 files changed, 43 insertions(+), 33 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 21b3f63..3a9b6d0 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -745,50 +745,50 @@ subroutine build_W(sys, cc_int, cc_amp, asym) ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed ! by a simple dgemm call - allocate(scratch, mold=W_oooo) + allocate(scratch,reshape_scratch, mold=W_oooo) ! Eq. 6: W_mnij = + P_(ij) \sum_e t_j^e + 1/2\sum_{ef} tau_ij^ef ! This performs the identity in the perm. operator - print*,'dgemm' - call dgemm_wrapper('N','T',nocc**3,nocc,nocc,cc_int%ooov,t1,scratch) + call dgemm_wrapper('N','T',nocc**3,nocc,nvirt,cc_int%ooov,t1,scratch) ! This adds to W_mnij W_oooo = cc_int%oooo + scratch ! This performs the i<->j swap in the perm. operator -! reshape_scratch = reshape(scratch, (/nocc,nocc,nocc,nocc/), order=(/1,2,4,3/)) -! W_oooo = W_oooo - reshape_scratch - W_oooo = W_oooo - reshape(scratch, (/nocc,nocc,nocc,nocc/), order=(/1,2,4,3/)) + reshape_scratch = reshape(scratch, shape(reshape_scratch), order=(/1,2,4,3/)) + W_oooo = W_oooo - reshape_scratch +! W_oooo = W_oooo - reshape(scratch, (/nocc,nocc,nocc,nocc/), order=(/1,2,4,3/)) ! This performs the last contraction ! reshape_scratch = reshape(tau, (/nvirt,nvirt,nocc,nocc/), order=(/3,4,1,2/)) - print*,'dgemm' - call dgemm_wrapper('N','N',nocc**2,nocc**2,nvirt**2,cc_int%oovv,& - reshape(tau, (/nvirt,nvirt,nocc,nocc/), order=(/3,4,1,2/)),scratch) + deallocate(reshape_scratch) + allocate(reshape_scratch(nvirt,nvirt,nocc,nocc)) + reshape_scratch = reshape(tau, shape(reshape_scratch), order=(/3,4,1,2/)) + call dgemm_wrapper('N','N',nocc**2,nocc**2,nvirt**2,cc_int%oovv,reshape_scratch,scratch) W_oooo = W_oooo + scratch/2 -! reshape_scratch = reshape(W_oooo, (/nocc,nocc,nocc,nocc/), order=(/3,4,1,2/)) - W_oooo = reshape(W_oooo, (/nocc,nocc,nocc,nocc/), order=(/3,4,1,2/)) + deallocate(reshape_scratch) + allocate(reshape_scratch, mold=W_oooo) + reshape_scratch = reshape(W_oooo, shape(reshape_scratch), order=(/3,4,1,2/)) +! W_oooo = reshape(W_oooo, (/nocc,nocc,nocc,nocc/), order=(/3,4,1,2/)) + W_oooo = reshape_scratch - deallocate(scratch) - allocate(scratch, mold=W_vvvv) + deallocate(scratch,reshape_scratch) + allocate(scratch,reshape_scratch, mold=W_vvvv) ! - P_(ab) t_m^b = + P_(ab) (t_b^m)^T , plus another sign change, which is most easily explained ! if we look at it by element: t_b^m = \sum_m t_b^m = -\sum_m t_b^m - print*,'dgemm' - call dgemm_wrapper('T','N',nocc,nvirt**3,nocc,t1,cc_int%ovvv,scratch) + call dgemm_wrapper('T','N',nvirt,nvirt**3,nocc,t1,cc_int%ovvv,scratch) W_vvvv = cc_int%vvvv - scratch -! reshape_scratch = reshape(scratch,(/nvirt,nvirt,nvirt,nvirt/),order=(/2,1,3,4/)) -! W_vvvv = W_vvvv + reshape_scratch - W_vvvv = W_vvvv + reshape(scratch,(/nvirt,nvirt,nvirt,nvirt/),order=(/2,1,3,4/)) -! reshape_scratch = reshape(W_vvvv,(/nvirt,nvirt,nvirt,nvirt/),order=(/3,4,1,2/)) -! W_vvvv = reshape_scratch - W_vvvv = reshape(W_vvvv,(/nvirt,nvirt,nvirt,nvirt/),order=(/3,4,1,2/)) - - deallocate(scratch) + reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) + W_vvvv = W_vvvv + reshape_scratch +! W_vvvv = W_vvvv + reshape(scratch,(/nvirt,nvirt,nvirt,nvirt/),order=(/2,1,3,4/)) + reshape_scratch = reshape(W_vvvv,shape(reshape_scratch),order=(/3,4,1,2/)) + W_vvvv = reshape_scratch +! W_vvvv = reshape(W_vvvv,(/nvirt,nvirt,nvirt,nvirt/),order=(/3,4,1,2/)) + + deallocate(scratch,reshape_scratch) allocate(scratch, mold=W_ovvo) - print*,'dgemm' - call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nocc,cc_int%ovvo,t1,scratch) + call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvo,t1,scratch) W_ovvo = cc_int%ovvo + scratch - print*,'dgemm' - call dgemm_wrapper('T','N',nocc,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) + call dgemm_wrapper('T','N',nvirt,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) W_ovvo = W_ovvo - scratch !$omp parallel default(none) & @@ -923,13 +923,10 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) allocate(tmp_t2_s, source=t2) ! t_ij^ae F_be - print*,'dgemm' - call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) + call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nocc,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s - print*,'dgemm' call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 - print*,'dgemm' call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 deallocate(tmp_t2_s) diff --git a/src/linalg.f90 b/src/linalg.f90 index 306632a..15e0f9f 100644 --- a/src/linalg.f90 +++ b/src/linalg.f90 @@ -62,9 +62,22 @@ subroutine dgemm_wrapper(transA, transB, outer_row, outer_col, inner_dim, A, B, integer, intent(in) :: outer_row, outer_col, inner_dim real(p), intent(in) :: A(*), B(*) real(p), intent(inout) :: C(*) - + integer :: LDA, LDB + + if (transA == 'T') then + LDA = inner_dim + else + LDA = outer_row + end if + + if (transB == 'T') then + LDB = outer_col + else + LDB = inner_dim + end if + call dgemm(transA, transB, outer_row, outer_col, inner_dim, 1.0_dp, & - A, outer_row, B, inner_dim, 0.0_dp, C, outer_row) + A, LDA, B, LDB, 0.0_dp, C, outer_row) end subroutine dgemm_wrapper elemental subroutine zero_mat(matel) From 836add38d3fd25b44eb5c346ddce7bd2d0fc7d0c Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 26 Jan 2022 01:17:38 +0000 Subject: [PATCH 55/71] Debugging attempt, comments and housekeeping. Still not getting correct CCSD energies. --- src/ccsd.f90 | 167 ++++++++++++++++++++++++++++++--------------------- 1 file changed, 97 insertions(+), 70 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 3a9b6d0..2a5e2a6 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -35,7 +35,7 @@ module ccsd ! These are identical as the HF-SCF ones, other than that we store and use the T matrices, ! instead of Fock matrices for error matrix computation. Also that we don't store the error matrices as that will - ! double the memory usage what is a fast step (compared to updating amplitudes) anyway. Instead we use the idx lookup array + ! double the memory usage in what is a fast step (compared to updating amplitudes) anyway. Instead we use the idx lookup array ! to make sure we take the right differences in computing e_i matrices on the fly. ! ! In more detail, as e_i = T_i+1 - T_i, and we overwrite T1 when T8 is the newest T matrix, we must make sure we never @@ -170,14 +170,14 @@ subroutine do_ccsd_spinorb(sys, int_store) allocate(cc_int%oooo, source=asym(1:nocc,1:nocc,1:nocc,1:nocc)) ! 3 occupied, 1 virtual, of which there are 3 types: ovoo, oovo, ooov, which are all related by permutational sym allocate(cc_int%ooov, source=asym(1:nocc,1:nocc,1:nocc,nocc+1:2*nbasis)) - cc_int%ovoo = reshape(cc_int%ooov, (/nocc,nvirt,nocc,nocc/), order=(/1,4,3,2/)) - cc_int%oovo = -reshape(cc_int%ooov, (/nocc,nocc,nvirt,nocc/), order=(/1,2,4,3/)) + allocate(cc_int%ovoo, source=asym(1:nocc,nocc+1:2*nbasis,1:nocc,1:nocc)) + allocate(cc_int%oovo, source=asym(1:nocc,1:nocc,nocc+1:2*nbasis,1:nocc)) ! 2o2v allocate(cc_int%oovv, source=asym(1:nocc,1:nocc,nocc+1:2*nbasis,nocc+1:2*nbasis)) - cc_int%ovvo = -reshape(cc_int%oovv, (/nocc,nvirt,nvirt,nocc/), order=(/1,4,3,2/)) + allocate(cc_int%ovvo, source=asym(1:nocc,nocc+1:2*nbasis,nocc+1:2*nbasis,1:nocc)) ! 1o3v allocate(cc_int%ovvv, source=asym(1:nocc,nocc+1:2*nbasis,nocc+1:2*nbasis,nocc+1:2*nbasis)) - cc_int%vovv = -reshape(cc_int%ovvv, (/nvirt,nocc,nvirt,nvirt/), order=(/2,1,3,4/)) + allocate(cc_int%vovv, source=asym(nocc+1:2*nbasis,1:nocc,nocc+1:2*nbasis,nocc+1:2*nbasis)) ! 4v allocate(cc_int%vvvv, source=asym(nocc+1:2*nbasis,nocc+1:2*nbasis,nocc+1:2*nbasis,nocc+1:2*nbasis)) @@ -187,7 +187,6 @@ subroutine do_ccsd_spinorb(sys, int_store) write(iunit, *) t0=t1 - ! [todo]: do we keep the unsliced, unrestricted asymmetrised ERI array? deallocate(int_store%asym_spinorb) end associate @@ -210,12 +209,12 @@ subroutine do_ccsd_spinorb(sys, int_store) ! ################### ! Iterative CC solver ! ################### - associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab, asym=>int_store%asym_spinorb) + associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) do iter = 1, maxiter ! Update intermediate tensors call build_tau(sys, cc_amp, cc_int) - call build_F(sys, cc_int, cc_amp, asym) - call build_W(sys, cc_int, cc_amp, asym) + call build_F(sys, cc_int, cc_amp) + call build_W(sys, cc_int, cc_amp) ! CC amplitude equations call update_amplitudes(sys, cc_amp, int_store, cc_int) @@ -375,8 +374,8 @@ subroutine do_ccsd_spatial(sys, int_store) do iter = 1, maxiter ! Update intermediate tensors call build_tau(sys, cc_amp, cc_int) - call build_F(sys, cc_int, cc_amp, asym) - call build_W(sys, cc_int, cc_amp, asym) + call build_F(sys, cc_int, cc_amp) + call build_W(sys, cc_int, cc_amp) ! CC amplitude equations call update_amplitudes(sys, cc_amp, int_store, cc_int) @@ -520,9 +519,9 @@ subroutine init_diis_cc_t(sys, diis) allocate(diis%idx(diis%n_errmat,2), source=0) associate(nvirt=>sys%nvirt, nocc=>sys%nocc) - allocate(diis%t1(diis%n_errmat,nocc,nvirt), source=0.0_p, stat=ierr) + allocate(diis%t1(nocc,nvirt,diis%n_errmat), source=0.0_p, stat=ierr) call check_allocate('diis%t1', diis%n_errmat*nocc*nvirt, ierr) - allocate(diis%t2(diis%n_errmat,nocc,nocc,nvirt,nvirt), source=0.0_p, stat=ierr) + allocate(diis%t2(nocc,nocc,nvirt,nvirt,diis%n_errmat), source=0.0_p, stat=ierr) call check_allocate('diis%t1', diis%n_errmat*(nocc*nvirt)**2, ierr) end associate end subroutine init_diis_cc_t @@ -541,13 +540,16 @@ subroutine update_diis_cc(diis, cc_amp) integer :: i, j, ierr + ! Increment counter diis%iter = diis%iter+1 + ! A modulo behaviour, but makes sure we never get iter = 0 if (diis%iter > diis%n_errmat) diis%iter = diis%iter - diis%n_errmat + ! In the first few iterations we need to make sure we don't accidentally access the empty arrays if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 - diis%t1(diis%iter,:,:) = 0.0_p - diis%t2(diis%iter,:,:,:,:) = 0.0_p - diis%t1(diis%iter,:,:) = cc_amp%t_ia - diis%t2(diis%iter,:,:,:,:) = cc_amp%t_ijab + + ! Store the current amplitudes + diis%t1(:,:,diis%iter) = cc_amp%t_ia + diis%t2(:,:,:,:,diis%iter) = cc_amp%t_ijab associate(n=>diis%n_active, nerr=>diis%n_errmat, it=>diis%iter, idx=>diis%idx) if (n > 2) then @@ -560,7 +562,8 @@ subroutine update_diis_cc(diis, cc_amp) ! So our idx array should look like ! 4 3 2 1 8 7 6 ! 3 2 1 8 7 6 5 - ! (note that the code below gives something like this but with the columns swapped around but that's ok) + ! (note that the code below gives something like this but with the columns swapped around but that's ok + ! since we don't care about chronological ordering) do i = 1, n-1 idx(i,1) = mod(it+i+1, n)+1 idx(i,2) = mod(it+i, n)+1 @@ -578,8 +581,8 @@ subroutine update_diis_cc(diis, cc_amp) do j = 1, i ! We compute the error matrices on the fly ! [TODO] - shift iter index to the end to give better cache behaviour - diis%B(i,j) = sum((diis%t1(idx(i,1),:,:)-diis%t1(idx(i,2),:,:))*(diis%t1(idx(j,1),:,:)-diis%t1(idx(j,2),:,:))) & - + sum((diis%t2(idx(i,1),:,:,:,:)-diis%t2(idx(i,2),:,:,:,:))*(diis%t2(idx(j,1),:,:,:,:)-diis%t2(idx(j,2),:,:,:,:))) + diis%B(i,j) = sum((diis%t1(:,:,idx(i,1))-diis%t1(:,:,idx(i,2)))*(diis%t1(:,:,idx(j,1))-diis%t1(:,:,idx(j,2)))) & + + sum((diis%t2(:,:,:,:,idx(i,1))-diis%t2(:,:,:,:,idx(i,2)))*(diis%t2(:,:,:,:,idx(j,1))-diis%t2(:,:,:,:,idx(j,2)))) end do end do call linsolve(diis%B, diis%c, ierr) @@ -587,8 +590,8 @@ subroutine update_diis_cc(diis, cc_amp) cc_amp%t_ia = 0.0_p cc_amp%t_ijab = 0.0_p do i = 1, n - cc_amp%t_ia = cc_amp%t_ia + diis%c(i) * diis%t1(i,:,:) - cc_amp%t_ijab = cc_amp%t_ijab + diis%c(i) * diis%t2(i,:,:,:,:) + cc_amp%t_ia = cc_amp%t_ia + diis%c(i) * diis%t1(:,:,i) + cc_amp%t_ijab = cc_amp%t_ijab + diis%c(i) * diis%t2(:,:,:,:,i) end do end if end associate @@ -644,19 +647,17 @@ subroutine build_tau(sys, cc_amp, cc_int) end subroutine build_tau - subroutine build_F(sys, cc_int, cc_amp, asym) + subroutine build_F(sys, cc_int, cc_amp) ! Build the two-index F intermediates, ! Eqs. 3-5, note as we use HF reference all terms involving the fock matrix vanishes. ! In: ! sys: System under study. ! cc_amp: CC amplitudes - ! asym: the antisymmetrised two-electron integrals ! In/out: ! cc_int: CC intermediates with the F matrices updated. type(system_t), intent(in) :: sys type(cc_amp_t), intent(in) :: cc_amp - real(p), intent(in) :: asym(:,:,:,:) type(cc_int_t), intent(inout) :: cc_int integer :: a, e, f, m, n, i @@ -670,7 +671,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) !$omp parallel default(none) & !$omp private(a, e, f, m, n, i) & - !$omp shared(sys, cc_int, cc_amp, asym) + !$omp shared(sys, cc_int, cc_amp) ! F_ae = \sum_{mf} t_m^f * - 0.5 \sum_{mnf} \tau~_{mn}^{af} !$omp do schedule(static, 10) collapse(2) @@ -696,7 +697,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) do n = 1, nocc F_oo(m,i) = F_oo(m,i) - t_ia(n,e)*cc_int%ooov(n,m,i,e) ! [todo] - This is terrible cache-wise, but does it warrant creating a new slice/doing a reshape? - F_oo(m,i) = F_oo(m,i) - 0.5*dot_product(tau_tilde(n,i,:,e),cc_int%oovv(m,n,e,:)) + F_oo(m,i) = F_oo(m,i) + 0.5*dot_product(tau_tilde(n,i,:,e),cc_int%oovv(m,n,e,:)) end do end do end do @@ -705,8 +706,8 @@ subroutine build_F(sys, cc_int, cc_amp, asym) ! F_me = \sum_{nf} t_n^f * !$omp do schedule(static, 10) collapse(2) - do m = 1, nocc - do e = 1, nvirt + do e = 1, nvirt + do m = 1, nocc ! [todo] - same as above, also investigate if sum(A*B) is better in cases of missed cache F_ov(m,e) = F_ov(m,e) + sum(t_ia(:,:)*cc_int%oovv(m,:,e,:)) end do @@ -716,7 +717,7 @@ subroutine build_F(sys, cc_int, cc_amp, asym) end associate end subroutine build_F - subroutine build_W(sys, cc_int, cc_amp, asym) + subroutine build_W(sys, cc_int, cc_amp) ! Build the four-index W intermediates, Eqs. 6 and 8. ! Note that we use a factor of 0.5 in the innermost line of the W_oooo loop instead of 0.25 per main text of Stanton, ! this is to make allowance for when W_vvvv cannot be stored due to memory limitation and has to be computed on the fly. @@ -724,7 +725,6 @@ subroutine build_W(sys, cc_int, cc_amp, asym) ! In: ! sys: System under study. ! cc_amp: CC amplitudes - ! asym: the antisymmetrised two-electron integrals ! In/out: ! cc_int: CC intermediates with the F matrices updated. @@ -732,7 +732,6 @@ subroutine build_W(sys, cc_int, cc_amp, asym) type(system_t), intent(in) :: sys type(cc_amp_t), intent(in) :: cc_amp - real(p), intent(in) :: asym(:,:,:,:) type(cc_int_t), intent(inout) :: cc_int integer :: m, n, i, j, e, f, b, a real(p) :: x @@ -740,60 +739,65 @@ subroutine build_W(sys, cc_int, cc_amp, asym) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, nvirt=>sys%nvirt, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab,& W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau, W_vvvv=>cc_int%W_vvvv) - W_oooo = 0.0_p - W_ovvo = 0.0_p ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed ! by a simple dgemm call allocate(scratch,reshape_scratch, mold=W_oooo) - ! Eq. 6: W_mnij = + P_(ij) \sum_e t_j^e + 1/2\sum_{ef} tau_ij^ef + ! ######################################################################################################################## + ! Eq. (6): W_mnij = + P_(ij) t_j^e + 1/2 tau_ij^ef + ! ######################################################################################################################## ! This performs the identity in the perm. operator call dgemm_wrapper('N','T',nocc**3,nocc,nvirt,cc_int%ooov,t1,scratch) - ! This adds to W_mnij W_oooo = cc_int%oooo + scratch ! This performs the i<->j swap in the perm. operator reshape_scratch = reshape(scratch, shape(reshape_scratch), order=(/1,2,4,3/)) W_oooo = W_oooo - reshape_scratch -! W_oooo = W_oooo - reshape(scratch, (/nocc,nocc,nocc,nocc/), order=(/1,2,4,3/)) - ! This performs the last contraction -! reshape_scratch = reshape(tau, (/nvirt,nvirt,nocc,nocc/), order=(/3,4,1,2/)) deallocate(reshape_scratch) allocate(reshape_scratch(nvirt,nvirt,nocc,nocc)) + ! 1/2 tau_ijef reshape_scratch = reshape(tau, shape(reshape_scratch), order=(/3,4,1,2/)) call dgemm_wrapper('N','N',nocc**2,nocc**2,nvirt**2,cc_int%oovv,reshape_scratch,scratch) W_oooo = W_oooo + scratch/2 deallocate(reshape_scratch) allocate(reshape_scratch, mold=W_oooo) reshape_scratch = reshape(W_oooo, shape(reshape_scratch), order=(/3,4,1,2/)) -! W_oooo = reshape(W_oooo, (/nocc,nocc,nocc,nocc/), order=(/3,4,1,2/)) + ! We reshape it to W_ijmn to make contractions more amenable to dgemm W_oooo = reshape_scratch deallocate(scratch,reshape_scratch) allocate(scratch,reshape_scratch, mold=W_vvvv) - ! - P_(ab) t_m^b = + P_(ab) (t_b^m)^T , plus another sign change, which is most easily explained - ! if we look at it by element: t_b^m = \sum_m t_b^m = -\sum_m t_b^m + ! ######################################################################################################################## + ! Eq. (7): W_abef = - P_(ab)(t_mb) + ! ######################################################################################################################## + ! - P_(ab) t_m^b = + P_(ab) (t_b^m)^T call dgemm_wrapper('T','N',nvirt,nvirt**3,nocc,t1,cc_int%ovvv,scratch) - W_vvvv = cc_int%vvvv - scratch + W_vvvv = cc_int%vvvv + scratch reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) - W_vvvv = W_vvvv + reshape_scratch -! W_vvvv = W_vvvv + reshape(scratch,(/nvirt,nvirt,nvirt,nvirt/),order=(/2,1,3,4/)) + W_vvvv = W_vvvv - reshape_scratch reshape_scratch = reshape(W_vvvv,shape(reshape_scratch),order=(/3,4,1,2/)) + ! We reshape it to W_efab to make contractions more amenable to dgemm W_vvvv = reshape_scratch -! W_vvvv = reshape(W_vvvv,(/nvirt,nvirt,nvirt,nvirt/),order=(/3,4,1,2/)) deallocate(scratch,reshape_scratch) allocate(scratch, mold=W_ovvo) - call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvo,t1,scratch) + ! ######################################################################################################################## + ! Eq. (8): W_mbej = + t_jf - t_nb - (1/2 t_jnfb + t_jf t_nb) + ! ######################################################################################################################## + ! + t_jf + call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvv,t1,scratch) W_ovvo = cc_int%ovvo + scratch + ! - t_nb = +(t_bn)^T call dgemm_wrapper('T','N',nvirt,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) - W_ovvo = W_ovvo - scratch + W_ovvo = W_ovvo + scratch + + deallocate(scratch) !$omp parallel default(none) & !$omp private(x) & - !$omp shared(cc_amp,asym,cc_int) + !$omp shared(cc_amp,cc_int) !$omp do schedule(static, 10) collapse(4) do j = 1, nocc do e = 1, nvirt @@ -833,7 +837,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) type(cc_amp_t), intent(inout) :: cc_amp type(cc_int_t), intent(inout) :: cc_int - real(p), allocatable :: tmp_t2_s(:,:,:,:) + real(p), dimension(:,:,:,:), allocatable :: tmp_t2_s, reshape_tmp integer :: i, j, a, b, m, n, e, f @@ -842,9 +846,14 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nvirt=>sys%nvirt,& W_vvvv=>cc_int%W_vvvv) + ! ######################################################################################################################## ! Update T1 + ! Eq. (1) D_ia t_i^a = t_ie F_ae - t_ma F_mi + t_imae F_me - t_nf -1/2 t_imef - 1/2 t_mnae + ! ######################################################################################################################## + ! #### t_ie F_ae tmp_t1 = matmul(t1,transpose(F_vv)) + ! #### -t_ma F_mi tmp_t1 = tmp_t1 - matmul(transpose(F_oo),t1) !$omp parallel default(none) & @@ -858,17 +867,21 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) do i = 1, nocc do m = 1, nocc do e = 1, nvirt + ! #### t_imae F_me tmp_t1(i,a) = tmp_t1(i,a) + t2(m,i,e,a)*F_ov(m,e) do f = 1, nvirt + ! #### -1/2 t_imef tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(m,i,f,e)*cc_int%ovvv(m,a,e,f) end do do n = 1, nocc + ! #### -1/2 t_mnae tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(n,m,e,a)*cc_int%oovo(n,m,e,i) end do end do end do do e = 1, nvirt do n = 1, nocc + ! #### -t_nf tmp_t1(i,a) = tmp_t1(i,a) - t1(n,e)*cc_int%oovv(n,i,a,e) end do end do @@ -879,7 +892,13 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) tmp_t1 = tmp_t1/D_ia + ! ######################################################################################################################## ! Update T2 + ! Eq. (2) D_ijab t_ijab = + P_ab(t_ijae (F_be - 1/2 t_mb F_me)) - P_(ij)(t_imab (F_mj + 1/2 t_je F_me)) + ! + 1/2 tau_mnab W_mnij + 1/2 tau_ijef W_abef + P_(ij)P_(ab)(t_imae W_mbej - t_ie t_ma ) + ! + P_(ij)(t_ie) - P_(ab)(t_ma ) + ! ######################################################################################################################## + ! tmp_t2 = cc_int%oovv !$omp parallel default(none) & !$omp shared(sys, cc_amp, int_store, cc_int) @@ -888,29 +907,26 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) do a = 1, nvirt do j = 1, nocc do i = 1, nocc - do e = 1, nvirt - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(j,i,e,b)*F_vv(a,e) & - + tmp_t1(i,e)*cc_int%vovv(e,j,a,b) - tmp_t1(j,e)*cc_int%vovv(e,i,a,b) - do m = 1, nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*F_ov(m,e)*t2(i,j,b,e)*tmp_t1(m,a) - end do - end do do m = 1, nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(m,i,b,a)*F_oo(m,j) + t2(m,j,b,a)*F_oo(m,i) & - - tmp_t1(m,a)*cc_int%ovoo(m,b,i,j) + tmp_t1(m,b)*cc_int%ovoo(m,a,i,j) + ! [todo]: this can be cast into dgemm form + ! -P_(ij)(t_imab F_mj) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(m,i,b,a)*F_oo(m,j) + t2(m,j,b,a)*F_oo(m,i) do e = 1, nvirt - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*tmp_t1(j,e)-& - t2(j,m,a,b)*tmp_t1(i,e)) + ! -1/2 P_(ij)(t_je F_me t_imab) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*t1(j,e)-& + t2(j,m,a,b)*t1(i,e)) end do end do do m = 1, nocc do e = 1, nvirt + ! P_(ij)P_(ab)(t_imae W_mbej - t_ie t_ma ) + ! [todo]: Maybe one of the permutations is good for dgemm, then the rest can be reshaped? tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & - + t2(m,i,e,a)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*cc_int%oovv(m,j,e,b)& - - t2(m,j,e,a)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*cc_int%oovv(m,i,e,b)& - - t2(m,i,e,b)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*cc_int%oovv(m,j,e,a)& - + t2(m,j,e,b)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*cc_int%oovv(m,i,e,a) + + t2(m,i,e,a)*W_ovvo(m,b,e,j) - t1(i,e)*t1(m,a)*cc_int%oovv(m,j,e,b)& + - t2(m,j,e,a)*W_ovvo(m,b,e,i) + t1(j,e)*t1(m,a)*cc_int%oovv(m,i,e,b)& + - t2(m,i,e,b)*W_ovvo(m,a,e,j) + t1(i,e)*t1(m,b)*cc_int%oovv(m,j,e,a)& + + t2(m,j,e,b)*W_ovvo(m,a,e,i) - t1(j,e)*t1(m,b)*cc_int%oovv(m,i,e,a) end do end do end do @@ -920,13 +936,24 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) !$omp end do !$omp end parallel - allocate(tmp_t2_s, source=t2) - - ! t_ij^ae F_be - call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nocc,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) - tmp_t2 = tmp_t2 + tmp_t2_s + allocate(tmp_t2_s, reshape_tmp, source=t2) + + ! P_(ab)(t_ijae (F_be - 1/2 t_mb F_me)) + call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) + tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + ! P_(ij)(t_ie) = P_(ij)(t_ie) + call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nvirt,t1,cc_int%vovv,tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) + tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + ! -P_(ab)(t_ma ) = +P_(ab)( t_ma) + call dgemm_wrapper('N','N',nocc**2*nvirt,nvirt,nocc,cc_int%oovo,t1,tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) + tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + ! + 1/2 tau_mnab W_mnij, but remember out W_mnij is reshaped as W_ijmn call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 + ! + 1/2 tau_ijef W_abef call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 deallocate(tmp_t2_s) From 6324a94bf528a154f9f4095fbc11ae29b2a4bdd4 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 26 Jan 2022 15:28:52 +0000 Subject: [PATCH 56/71] Fix diis idx bug (no help with the energy though), enable input file specification of number of error matrices, documentation --- CMakeLists.txt | 8 ++-- dat/els.in | 12 ++--- src/ccsd.f90 | 112 +++++++++++++++++++++++++--------------------- src/hf.f90 | 15 +++++-- src/integrals.f90 | 4 ++ src/system.f90 | 9 ++-- 6 files changed, 92 insertions(+), 68 deletions(-) diff --git a/CMakeLists.txt b/CMakeLists.txt index 969ca64..7b46971 100644 --- a/CMakeLists.txt +++ b/CMakeLists.txt @@ -7,12 +7,12 @@ project (els) enable_language (Fortran) if (CMAKE_Fortran_COMPILER_ID MATCHES "GNU") - set (dialect "-ffree-form -std=f2008 -fimplicit-none -fopenmp") - set (extras "-fcheck=all -ggdb") + set (dialect "-ffree-form -std=f2008 -fimplicit-none -fopenmp -O3") + set (extras "-fcheck=all -Wall -ggdb -O0") endif () if (CMAKE_Fortran_COMPILER_ID MATCHES "Intel") - set (dialect "-stand f08 -free -implicitnone -qopenmp") - set (extras "-check bounds") + set (dialect "-stand f08 -free -implicitnone -qopenmp -O3") + set (extras "-check bounds -O0") endif () set (CMAKE_Fortran_FLAGS_DEBUG "${CMAKE_Fortran_FLAGS_DEBUG} ${extras}") diff --git a/dat/els.in b/dat/els.in index bc0e85e..4c518a4 100644 --- a/dat/els.in +++ b/dat/els.in @@ -1,7 +1,9 @@ &elsinput -calc_type="CCSD(T)_spinorb", -scf_e_tol=1e-7, -scf_d_tol=1e-6, -ccsd_e_tol=1e-7, -ccsd_t_tol=1e-6 +calc_type="CCSD_spinorb", +scf_e_tol=1e-6, +scf_d_tol=1e-7, +scf_diis_n_errmat=6, +ccsd_e_tol=1e-6, +ccsd_t_tol=1e-7, +ccsd_diis_n_errmat=8 / diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 2a5e2a6..c53a310 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -42,6 +42,7 @@ module ccsd ! subtract the newest T matrix with the oldest T matrix, and since doing that is tricky in a loop we keep the idx lookup array ! [TODO]: kick the slowest index to the last! + logical :: use_diis = .true. integer :: n_errmat = 8 integer :: n_active = 0 integer :: iter = 0 @@ -65,7 +66,7 @@ subroutine do_ccsd_spinorb(sys, int_store) type(system_t), intent(inout) :: sys type(int_store_t), intent(inout) :: int_store - integer :: i, j, a, b, p, q, r, s + integer :: i, j, k, a, b, p, q, r, s integer :: pr, qr, pa, pb, qa, qb, ra, rb, sa, sb real(dp) :: prqs, psqr real(dp) :: err @@ -241,7 +242,7 @@ subroutine do_ccsd_spinorb(sys, int_store) ! Nonlazy deallocations deallocate(st%t2_old) call deallocate_cc_int_t(cc_int) - call deallocate_diis_cc_t(diis) + if (diis%use_diis) call deallocate_diis_cc_t(diis) end subroutine do_ccsd_spinorb @@ -516,14 +517,23 @@ subroutine init_diis_cc_t(sys, diis) integer :: ierr - allocate(diis%idx(diis%n_errmat,2), source=0) + diis%n_errmat = sys%ccsd_diis_n_errmat - associate(nvirt=>sys%nvirt, nocc=>sys%nocc) - allocate(diis%t1(nocc,nvirt,diis%n_errmat), source=0.0_p, stat=ierr) - call check_allocate('diis%t1', diis%n_errmat*nocc*nvirt, ierr) - allocate(diis%t2(nocc,nocc,nvirt,nvirt,diis%n_errmat), source=0.0_p, stat=ierr) - call check_allocate('diis%t1', diis%n_errmat*(nocc*nvirt)**2, ierr) - end associate + if (diis%n_errmat < 2) then + ! Switch off diis + diis%use_diis = .false. + else + allocate(diis%idx(diis%n_errmat-1,2), source=0) + + diis%iter = 0; diis%n_active = 0 + + associate(nvirt=>sys%nvirt, nocc=>sys%nocc) + allocate(diis%t1(nocc,nvirt,diis%n_errmat), source=0.0_p, stat=ierr) + call check_allocate('diis%t1', diis%n_errmat*nocc*nvirt, ierr) + allocate(diis%t2(nocc,nocc,nvirt,nvirt,diis%n_errmat), source=0.0_p, stat=ierr) + call check_allocate('diis%t1', diis%n_errmat*(nocc*nvirt)**2, ierr) + end associate + end if end subroutine init_diis_cc_t subroutine update_diis_cc(diis, cc_amp) @@ -540,13 +550,13 @@ subroutine update_diis_cc(diis, cc_amp) integer :: i, j, ierr + if (diis%use_diis) then ! Increment counter diis%iter = diis%iter+1 ! A modulo behaviour, but makes sure we never get iter = 0 if (diis%iter > diis%n_errmat) diis%iter = diis%iter - diis%n_errmat ! In the first few iterations we need to make sure we don't accidentally access the empty arrays if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 - ! Store the current amplitudes diis%t1(:,:,diis%iter) = cc_amp%t_ia diis%t2(:,:,:,:,diis%iter) = cc_amp%t_ijab @@ -565,8 +575,10 @@ subroutine update_diis_cc(diis, cc_amp) ! (note that the code below gives something like this but with the columns swapped around but that's ok ! since we don't care about chronological ordering) do i = 1, n-1 - idx(i,1) = mod(it+i+1, n)+1 - idx(i,2) = mod(it+i, n)+1 + idx(i,1) = it + 1 - i + if (idx(i,1) < 1) idx(i,1) = idx(i,1) + n + idx(i,2) = it - i + if (idx(i,2) < 1) idx(i,2) = idx(i,2) + n end do ! Construct the B matrix if (n <= nerr) then @@ -579,8 +591,7 @@ subroutine update_diis_cc(diis, cc_amp) diis%c = diis%rhs do i = 1, n-1 do j = 1, i - ! We compute the error matrices on the fly - ! [TODO] - shift iter index to the end to give better cache behaviour + ! We compute the error matrices on the fly, linsolve/dsysv only need the upper triangle diis%B(i,j) = sum((diis%t1(:,:,idx(i,1))-diis%t1(:,:,idx(i,2)))*(diis%t1(:,:,idx(j,1))-diis%t1(:,:,idx(j,2)))) & + sum((diis%t2(:,:,:,:,idx(i,1))-diis%t2(:,:,:,:,idx(i,2)))*(diis%t2(:,:,:,:,idx(j,1))-diis%t2(:,:,:,:,idx(j,2)))) end do @@ -595,6 +606,9 @@ subroutine update_diis_cc(diis, cc_amp) end do end if end associate + else + continue + end if end subroutine update_diis_cc subroutine deallocate_diis_cc_t(diis) @@ -620,22 +634,21 @@ subroutine build_tau(sys, cc_amp, cc_int) type(cc_int_t), intent(inout) :: cc_int integer :: i, j, a, b - real(p) :: ia, ja, x + real(p) :: x associate(nvirt=>sys%nvirt, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab,& tau=>cc_int%tau, tau_tilde=>cc_int%tau_tilde) tau = 0.0_p tau_tilde = 0.0_p !$omp parallel do default(none) & - !$omp private(i,j,a,b,ia,ja,x) & + !$omp private(i,j,a,b,x) & !$omp shared(sys, cc_amp, cc_int) & !$omp schedule(static, 10) collapse(2) do b = 1, nvirt do a = 1, nvirt do j = 1, nocc - ja = t_ia(j,a) do i = 1, nocc - x = t_ia(i,a)*t_ia(j,b) - t_ia(i,b)*ja + x = t_ia(i,a)*t_ia(j,b) - t_ia(i,b)*t_ia(j,a) tau_tilde(i,j,a,b) = t_ijab(i,j,a,b) + 0.5*x tau(i,j,a,b) = tau_tilde(i,j,a,b) + 0.5*x end do @@ -695,9 +708,9 @@ subroutine build_F(sys, cc_int, cc_amp) do i = 1, nocc do e = 1, nvirt do n = 1, nocc - F_oo(m,i) = F_oo(m,i) - t_ia(n,e)*cc_int%ooov(n,m,i,e) ! [todo] - This is terrible cache-wise, but does it warrant creating a new slice/doing a reshape? - F_oo(m,i) = F_oo(m,i) + 0.5*dot_product(tau_tilde(n,i,:,e),cc_int%oovv(m,n,e,:)) + F_oo(m,i) = F_oo(m,i) + 0.5*dot_product(tau_tilde(n,i,:,e),cc_int%oovv(m,n,e,:)) & + - t_ia(n,e)*cc_int%ooov(n,m,i,e) end do end do end do @@ -734,7 +747,6 @@ subroutine build_W(sys, cc_int, cc_amp) type(cc_amp_t), intent(in) :: cc_amp type(cc_int_t), intent(inout) :: cc_int integer :: m, n, i, j, e, f, b, a - real(p) :: x real(p), dimension(:,:,:,:), allocatable :: scratch, reshape_scratch associate(nbasis=>sys%nbasis, nocc=>sys%nocc, nvirt=>sys%nvirt, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab,& @@ -747,56 +759,54 @@ subroutine build_W(sys, cc_int, cc_amp) ! ######################################################################################################################## ! Eq. (6): W_mnij = + P_(ij) t_j^e + 1/2 tau_ij^ef ! ######################################################################################################################## - ! This performs the identity in the perm. operator + ! + P_(ij) t_j^e call dgemm_wrapper('N','T',nocc**3,nocc,nvirt,cc_int%ooov,t1,scratch) - W_oooo = cc_int%oooo + scratch - ! This performs the i<->j swap in the perm. operator reshape_scratch = reshape(scratch, shape(reshape_scratch), order=(/1,2,4,3/)) - W_oooo = W_oooo - reshape_scratch + W_oooo = cc_int%oooo + scratch - reshape_scratch deallocate(reshape_scratch) - allocate(reshape_scratch(nvirt,nvirt,nocc,nocc)) + ! 1/2 tau_ijef + allocate(reshape_scratch(nvirt,nvirt,nocc,nocc)) reshape_scratch = reshape(tau, shape(reshape_scratch), order=(/3,4,1,2/)) call dgemm_wrapper('N','N',nocc**2,nocc**2,nvirt**2,cc_int%oovv,reshape_scratch,scratch) W_oooo = W_oooo + scratch/2 deallocate(reshape_scratch) + + ! We reshape it to W_ijmn to make contractions more amenable to dgemm allocate(reshape_scratch, mold=W_oooo) reshape_scratch = reshape(W_oooo, shape(reshape_scratch), order=(/3,4,1,2/)) - ! We reshape it to W_ijmn to make contractions more amenable to dgemm W_oooo = reshape_scratch - deallocate(scratch,reshape_scratch) - allocate(scratch,reshape_scratch, mold=W_vvvv) ! ######################################################################################################################## ! Eq. (7): W_abef = - P_(ab)(t_mb) ! ######################################################################################################################## - ! - P_(ab) t_m^b = + P_(ab) (t_b^m)^T + ! @@@ - P_(ab) t_m^b = + P_(ab) (t_b^m)^T + allocate(scratch,reshape_scratch, mold=W_vvvv) call dgemm_wrapper('T','N',nvirt,nvirt**3,nocc,t1,cc_int%ovvv,scratch) - W_vvvv = cc_int%vvvv + scratch reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) - W_vvvv = W_vvvv - reshape_scratch - reshape_scratch = reshape(W_vvvv,shape(reshape_scratch),order=(/3,4,1,2/)) + W_vvvv = cc_int%vvvv + scratch - reshape_scratch + ! We reshape it to W_efab to make contractions more amenable to dgemm + reshape_scratch = reshape(W_vvvv,shape(reshape_scratch),order=(/3,4,1,2/)) W_vvvv = reshape_scratch - deallocate(scratch,reshape_scratch) - allocate(scratch, mold=W_ovvo) ! ######################################################################################################################## ! Eq. (8): W_mbej = + t_jf - t_nb - (1/2 t_jnfb + t_jf t_nb) ! ######################################################################################################################## ! + t_jf + allocate(scratch, mold=W_ovvo) call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvv,t1,scratch) W_ovvo = cc_int%ovvo + scratch - ! - t_nb = +(t_bn)^T + + ! @@@ - t_nb = +(t_bn)^T call dgemm_wrapper('T','N',nvirt,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) W_ovvo = W_ovvo + scratch - deallocate(scratch) + ! - (1/2 t_jnfb + t_jf t_nb) !$omp parallel default(none) & - !$omp private(x) & !$omp shared(cc_amp,cc_int) !$omp do schedule(static, 10) collapse(4) do j = 1, nocc @@ -804,10 +814,9 @@ subroutine build_W(sys, cc_int, cc_amp) do b = 1, nvirt do m = 1, nocc do n = 1, nocc - x = t1(n,b) do f = 1, nvirt ! [todo]: bad cache behaviour (last term), however dgemm isn't that much better herem since two reshapes needed. - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + x*t1(j,f)) * cc_int%oovv(m,n,e,f) + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + t1(n,b)*t1(j,f)) * cc_int%oovv(m,n,e,f) end do end do end do @@ -882,7 +891,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) do e = 1, nvirt do n = 1, nocc ! #### -t_nf - tmp_t1(i,a) = tmp_t1(i,a) - t1(n,e)*cc_int%oovv(n,i,a,e) + tmp_t1(i,a) = tmp_t1(i,a) + t1(n,e)*cc_int%ovvo(n,a,e,i) end do end do end do @@ -918,15 +927,15 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do end do - do m = 1, nocc - do e = 1, nvirt + do e = 1, nvirt + do m = 1, nocc ! P_(ij)P_(ab)(t_imae W_mbej - t_ie t_ma ) ! [todo]: Maybe one of the permutations is good for dgemm, then the rest can be reshaped? tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & - + t2(m,i,e,a)*W_ovvo(m,b,e,j) - t1(i,e)*t1(m,a)*cc_int%oovv(m,j,e,b)& - - t2(m,j,e,a)*W_ovvo(m,b,e,i) + t1(j,e)*t1(m,a)*cc_int%oovv(m,i,e,b)& - - t2(m,i,e,b)*W_ovvo(m,a,e,j) + t1(i,e)*t1(m,b)*cc_int%oovv(m,j,e,a)& - + t2(m,j,e,b)*W_ovvo(m,a,e,i) - t1(j,e)*t1(m,b)*cc_int%oovv(m,i,e,a) + + t2(m,i,e,a)*W_ovvo(m,b,e,j) - t1(i,e)*t1(m,a)*cc_int%ovvo(m,b,e,j)& + - t2(m,j,e,a)*W_ovvo(m,b,e,i) + t1(j,e)*t1(m,a)*cc_int%ovvo(m,b,e,i)& + - t2(m,i,e,b)*W_ovvo(m,a,e,j) + t1(i,e)*t1(m,b)*cc_int%ovvo(m,a,e,j)& + + t2(m,j,e,b)*W_ovvo(m,a,e,i) - t1(j,e)*t1(m,b)*cc_int%ovvo(m,a,e,i) end do end do end do @@ -936,17 +945,16 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) !$omp end do !$omp end parallel - allocate(tmp_t2_s, reshape_tmp, source=t2) - ! P_(ab)(t_ijae (F_be - 1/2 t_mb F_me)) - call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) + allocate(tmp_t2_s, reshape_tmp, source=t2) + call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,(F_vv-0.5*matmul(transpose(t1),F_ov)),tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp ! P_(ij)(t_ie) = P_(ij)(t_ie) call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nvirt,t1,cc_int%vovv,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp - ! -P_(ab)(t_ma ) = +P_(ab)( t_ma) + ! @@@ -P_(ab)(t_ma ) = +P_(ab)( t_ma) call dgemm_wrapper('N','N',nocc**2*nvirt,nvirt,nocc,cc_int%oovo,t1,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp @@ -956,7 +964,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) ! + 1/2 tau_ijef W_abef call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 - deallocate(tmp_t2_s) + deallocate(tmp_t2_s, reshape_tmp) t1 = tmp_t1 t2 = tmp_t2/D_ijab diff --git a/src/hf.f90 b/src/hf.f90 index b8154f9..4a78aad 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -5,6 +5,7 @@ module hf type diis_t ! Contains matrices for use in the DIIS procedure + logical :: use_diis = .true. integer :: n_errmat = 6 integer :: n_active = 0 integer :: iter = 0 @@ -180,10 +181,16 @@ subroutine init_diis_t(sys, diis) type(system_t), intent(in) :: sys type(diis_t), intent(out) :: diis - associate(n=>sys%nbasis) - allocate(diis%e(diis%n_errmat,n,n), source=0.0_p) - allocate(diis%F(diis%n_errmat,n,n), source=0.0_p) - end associate + diis%n_errmat = sys%scf_diis_n_errmat + + if (diis%n_errmat <2 ) then + diis%use_diis = .false. + else + associate(n=>sys%nbasis) + allocate(diis%e(diis%n_errmat,n,n), source=0.0_p) + allocate(diis%F(diis%n_errmat,n,n), source=0.0_p) + end associate + end if end subroutine init_diis_t subroutine deallocate_diis_t(diis) diff --git a/src/integrals.f90 b/src/integrals.f90 index 006c932..09e7cc3 100644 --- a/src/integrals.f90 +++ b/src/integrals.f90 @@ -213,6 +213,10 @@ subroutine print_sys_info(sys, int_store) write(iunit, '(1X, A, 1X, I0)') 'Number of electrons:', sys%nel write(iunit, '(1X, A, 1X, I0)') 'Number of basis functions:', sys%nbasis write(iunit, '(1X, A, 1X, ES15.8)') 'E_nuc:', int_store%e_nuc + write(iunit, '(1X, A, 1X, ES8.2)') 'scf_e_tol:', sys%scf_e_tol + write(iunit, '(1X, A, 1X, ES8.2)') 'scf_d_tol:', sys%scf_d_tol + write(iunit, '(1X, A, 1X, ES8.2)') 'ccsd_e_tol:', sys%ccsd_e_tol + write(iunit, '(1X, A, 1X, ES8.2)') 'ccsd_t_tol:', sys%ccsd_t_tol end subroutine print_sys_info diff --git a/src/system.f90 b/src/system.f90 index 0fe5175..fcf3bd3 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -35,8 +35,10 @@ module system ! Tolerances real(p) :: scf_e_tol = 1e-6 real(p) :: scf_d_tol = 1e-6 + integer :: scf_diis_n_errmat = 6 real(p) :: ccsd_e_tol = 1e-6 real(p) :: ccsd_t_tol = 1e-6 + integer :: ccsd_diis_n_errmat = 8 ! Level of theory (up to) logical :: restricted @@ -61,12 +63,13 @@ subroutine read_system_in(sys) use error_handling, only: error type(system_t), intent(inout) :: sys real(p) :: scf_e_tol, scf_d_tol, ccsd_e_tol, ccsd_t_tol + integer :: scf_diis_n_errmat, ccsd_diis_n_errmat character(40) :: calc_type integer :: ir, ierr ! Define namelist - namelist /elsinput/ calc_type, scf_e_tol, scf_d_tol, ccsd_e_tol, ccsd_t_tol + namelist /elsinput/ calc_type, scf_e_tol, scf_d_tol, scf_diis_n_errmat, ccsd_e_tol, ccsd_t_tol, ccsd_diis_n_errmat ! Check if file exists inquire(file='dat/els.in', iostat=ierr) @@ -80,8 +83,8 @@ subroutine read_system_in(sys) close(ir) - sys%scf_e_tol = scf_e_tol; sys%scf_d_tol = scf_d_tol - sys%ccsd_e_tol = ccsd_e_tol; sys%ccsd_t_tol = ccsd_t_tol + sys%scf_e_tol = scf_e_tol; sys%scf_d_tol = scf_d_tol; sys%scf_diis_n_errmat = scf_diis_n_errmat + sys%ccsd_e_tol = ccsd_e_tol; sys%ccsd_t_tol = ccsd_t_tol; sys%ccsd_diis_n_errmat = ccsd_diis_n_errmat select case(trim(calc_type)) case("RHF") From bf1e73a866dea2cec37b17d6063b0c2196777b72 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 26 Jan 2022 15:56:27 +0000 Subject: [PATCH 57/71] Another CCSD DIIS bug spotted, still doesn't help --- src/ccsd.f90 | 8 ++++---- 1 file changed, 4 insertions(+), 4 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index c53a310..956f473 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -583,11 +583,11 @@ subroutine update_diis_cc(diis, cc_amp) ! Construct the B matrix if (n <= nerr) then if (allocated(diis%B)) deallocate(diis%B, diis%c, diis%rhs) - allocate(diis%B(n+1,n+1), diis%c(n+1), diis%rhs(n+1), source=0.0_p) + allocate(diis%B(n,n), diis%c(n), diis%rhs(n), source=0.0_p) end if - diis%B(n+1,:) = -1.0_p - diis%B(n+1,n+1) = 0.0_p - diis%rhs(n+1) = -1.0_p + diis%B(n,:) = -1.0_p + diis%B(n,n) = 0.0_p + diis%rhs(n) = -1.0_p diis%c = diis%rhs do i = 1, n-1 do j = 1, i From 07b8550df1af88089ef8f6f88872dc4dd64bba52 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Wed, 26 Jan 2022 16:10:50 +0000 Subject: [PATCH 58/71] Yet another DIIS bug, no help --- src/ccsd.f90 | 6 +++--- 1 file changed, 3 insertions(+), 3 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 956f473..a82ed20 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -600,9 +600,9 @@ subroutine update_diis_cc(diis, cc_amp) if (ierr /= 0) call error('ccsd::update_diis_cc', 'Linear solve failed!') cc_amp%t_ia = 0.0_p cc_amp%t_ijab = 0.0_p - do i = 1, n - cc_amp%t_ia = cc_amp%t_ia + diis%c(i) * diis%t1(:,:,i) - cc_amp%t_ijab = cc_amp%t_ijab + diis%c(i) * diis%t2(:,:,:,:,i) + do i = 1, n-1 + cc_amp%t_ia = cc_amp%t_ia + diis%c(i) * diis%t1(:,:,idx(i,1)) + cc_amp%t_ijab = cc_amp%t_ijab + diis%c(i) * diis%t2(:,:,:,:,idx(i,1)) end do end if end associate From 06673ec86454e525a0cfec0631cbbc630cbb5966 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Thu, 27 Jan 2022 00:12:39 +0000 Subject: [PATCH 59/71] AB testing commit --- src/ccsd.f90 | 168 ++++++++++++++++++++++++++++++++++++++++++++++++++- 1 file changed, 166 insertions(+), 2 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index a82ed20..a81a3f2 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -751,11 +751,11 @@ subroutine build_W(sys, cc_int, cc_amp) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, nvirt=>sys%nvirt, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab,& W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau, W_vvvv=>cc_int%W_vvvv) - + + if (.true.) then ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed ! by a simple dgemm call allocate(scratch,reshape_scratch, mold=W_oooo) - ! ######################################################################################################################## ! Eq. (6): W_mnij = + P_(ij) t_j^e + 1/2 tau_ij^ef ! ######################################################################################################################## @@ -804,6 +804,7 @@ subroutine build_W(sys, cc_int, cc_amp) call dgemm_wrapper('T','N',nvirt,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) W_ovvo = W_ovvo + scratch deallocate(scratch) + ! - (1/2 t_jnfb + t_jf t_nb) !$omp parallel default(none) & @@ -825,6 +826,72 @@ subroutine build_W(sys, cc_int, cc_amp) end do !$omp end do !$omp end parallel + + else + W_oooo = cc_int%oooo + W_ovvo = cc_int%ovvo + W_vvvv = cc_int%vvvv + !$omp parallel default(none) & + !$omp private(m, n, i, j, e, f, b, a) & + !$omp shared(sys, cc_int, cc_amp) + + ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed + ! by a simple dgemm call + !$omp do schedule(static, 10) collapse(4) + do n = 1, nocc + do m = 1, nocc + do j = 1, nocc + do i = 1, nocc + do e = 1, nvirt + W_oooo(i,j,m,n) = W_oooo(i,j,m,n) + t1(j,e)*cc_int%oovo(n,m,e,i) - t1(i,e)*cc_int%oovo(n,m,e,j) + do f = 1, nvirt + W_oooo(i,j,m,n) = W_oooo(i,j,m,n) - 0.5*t2(j,i,f,e)*cc_int%oovv(m,n,f,e) + end do + end do + end do + end do + end do + end do + !$omp end do + + ! [TODO]: make a switch to on-the-fly W_vvvv computation, for when memory is limited + ! Similarly, we order it (e,f,a,b) for the contraction tau_ij^ef W_abef + !$omp do schedule(static, 10) collapse(4) + do b = 1, nvirt + do a = 1, nvirt + do f = 1, nvirt + do e = 1, nvirt + do n = 1, nocc + W_vvvv(e,f,a,b) = W_vvvv(e,f,a,b) + t1(n,b)*cc_int%ovvv(n,a,e,f) - t1(n,a)*cc_int%ovvv(n,b,e,f) + end do + end do + end do + end do + end do + !$omp end do + + !$omp do schedule(static, 10) collapse(4) + do j = 1, nocc + do e = 1, nvirt + do b = 1, nvirt + do m = 1, nocc + do f = 1, nvirt + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - t1(j,f)*cc_int%ovvv(m,b,f,e) + end do + + do n = 1, nocc + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) + t1(n,b)*cc_int%oovo(n,m,e,j) + do f = 1, nvirt + W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + t1(n,b)*t1(j,f)) * cc_int%oovv(n,m,f,e) + end do + end do + end do + end do + end do + end do + !$omp end do + !$omp end parallel + end if end associate end subroutine build_W @@ -855,6 +922,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nvirt=>sys%nvirt,& W_vvvv=>cc_int%W_vvvv) + if (.false.) then ! ######################################################################################################################## ! Update T1 ! Eq. (1) D_ia t_i^a = t_ie F_ae - t_ma F_mi + t_imae F_me - t_nf -1/2 t_imef - 1/2 t_mnae @@ -968,6 +1036,102 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) t1 = tmp_t1 t2 = tmp_t2/D_ijab + + else + ! Update T1 + + tmp_t1 = matmul(t1,transpose(F_vv)) + tmp_t1 = tmp_t1 - matmul(transpose(F_oo),t1) + + !$omp parallel default(none) & + !$omp shared(sys, cc_amp, int_store, cc_int) + + ! Implied barrier here, better than master which doesn't have implied barrier + ! tmp_t1 can be shared as each loop iteration will update a unique element of it. + + !$omp do schedule(static, 10) collapse(2) + do a = 1, nvirt + do i = 1, nocc + do m = 1, nocc + do e = 1, nvirt + tmp_t1(i,a) = tmp_t1(i,a) + t2(m,i,e,a)*F_ov(m,e) + do f = 1, nvirt + tmp_t1(i,a) = tmp_t1(i,a) + 0.5*t2(m,i,f,e)*cc_int%ovvv(m,a,f,e) + end do + do n = 1, nocc + tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(n,m,e,a)*cc_int%oovo(n,m,e,i) + end do + end do + end do + do e = 1, nvirt + do n = 1, nocc + tmp_t1(i,a) = tmp_t1(i,a) + t1(n,e)*cc_int%ovvo(n,a,e,i) + end do + end do + end do + end do + !$omp end do + !$omp end parallel + + tmp_t1 = tmp_t1/D_ia + + ! Update T2 + + !$omp parallel default(none) & + !$omp shared(sys, cc_amp, int_store, cc_int) + !$omp do schedule(static, 10) collapse(4) + do b = 1, nvirt + do a = 1, nvirt + do j = 1, nocc + do i = 1, nocc + tmp_t2(i,j,a,b) = cc_int%oovv(i,j,a,b) + do e = 1, nvirt + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(j,i,e,b)*F_vv(a,e) & + - t1(i,e)*cc_int%ovvv(j,e,a,b) + t1(j,e)*cc_int%ovvv(i,e,a,b) + do m = 1, nocc + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*F_ov(m,e)*t2(i,j,b,e)*t1(m,a) + end do + end do + do m = 1, nocc + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(m,i,b,a)*F_oo(m,j) + t2(m,j,b,a)*F_oo(m,i) & + - t1(m,a)*cc_int%ovoo(m,b,i,j) + t1(m,b)*cc_int%ovoo(m,a,i,j) + do e = 1, nvirt + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*t1(j,e)-& + t2(j,m,a,b)*t1(i,e)) + end do + end do + + do m = 1, nocc + do e = 1, nvirt + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & + + t2(m,i,e,a)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*cc_int%ovvo(m,b,e,j)& + - t2(m,j,e,a)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*cc_int%ovvo(m,b,e,i)& + - t2(m,i,e,b)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*cc_int%ovvo(m,a,e,j)& + + t2(m,j,e,b)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*cc_int%ovvo(m,a,e,i) + end do + end do + end do + end do + end do + end do + !$omp end do + !$omp end parallel + + allocate(tmp_t2_s, source=t2) + + ! t_ij^ae F_be + call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) + tmp_t2 = tmp_t2 + tmp_t2_s + call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2_s) + tmp_t2 = tmp_t2 + tmp_t2_s/2 + call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2_s) + tmp_t2 = tmp_t2 + tmp_t2_s/2 + deallocate(tmp_t2_s) + + t1 = tmp_t1 + t2 = tmp_t2/D_ijab + + end if end associate end subroutine update_amplitudes From 3c09631c73ebd31b1becb2fe7baad0ce1983e026 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Thu, 27 Jan 2022 01:00:50 +0000 Subject: [PATCH 60/71] AB testing completed. Energies now correct. --- src/ccsd.f90 | 123 +++++++++++++++++++++++++++++---------------------- 1 file changed, 71 insertions(+), 52 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index a81a3f2..c7fbe6d 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -752,7 +752,7 @@ subroutine build_W(sys, cc_int, cc_amp) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, nvirt=>sys%nvirt, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab,& W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau, W_vvvv=>cc_int%W_vvvv) - if (.true.) then + if (.false.) then ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed ! by a simple dgemm call allocate(scratch,reshape_scratch, mold=W_oooo) @@ -828,58 +828,64 @@ subroutine build_W(sys, cc_int, cc_amp) !$omp end parallel else - W_oooo = cc_int%oooo - W_ovvo = cc_int%ovvo - W_vvvv = cc_int%vvvv + + allocate(scratch,reshape_scratch, mold=W_oooo) + ! ######################################################################################################################## + ! Eq. (6): W_mnij = + P_(ij) t_j^e + 1/2 tau_ij^ef + ! ######################################################################################################################## + ! + P_(ij) t_j^e + call dgemm_wrapper('N','T',nocc**3,nocc,nvirt,cc_int%ooov,t1,scratch) + reshape_scratch = reshape(scratch, shape(reshape_scratch), order=(/1,2,4,3/)) + W_oooo = cc_int%oooo + scratch - reshape_scratch + deallocate(reshape_scratch) + + ! 1/2 tau_ijef + allocate(reshape_scratch(nvirt,nvirt,nocc,nocc)) + reshape_scratch = reshape(tau, shape(reshape_scratch), order=(/3,4,1,2/)) + call dgemm_wrapper('N','N',nocc**2,nocc**2,nvirt**2,cc_int%oovv,reshape_scratch,scratch) + W_oooo = W_oooo + scratch/2 + deallocate(reshape_scratch) + + ! We reshape it to W_ijmn to make contractions more amenable to dgemm + allocate(reshape_scratch, mold=W_oooo) + reshape_scratch = reshape(W_oooo, shape(reshape_scratch), order=(/3,4,1,2/)) + W_oooo = reshape_scratch + deallocate(scratch,reshape_scratch) + + ! ######################################################################################################################## + ! Eq. (7): W_abef = - P_(ab)(t_mb) + ! ######################################################################################################################## + ! [todo]: explain the signs!! + allocate(scratch,reshape_scratch, mold=W_vvvv) + call dgemm_wrapper('T','N',nvirt,nvirt**3,nocc,t1,cc_int%ovvv,scratch) + reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) + W_vvvv = cc_int%vvvv - scratch + reshape_scratch + + ! We reshape it to W_efab to make contractions more amenable to dgemm + reshape_scratch = reshape(W_vvvv,shape(reshape_scratch),order=(/3,4,1,2/)) + W_vvvv = reshape_scratch + deallocate(scratch,reshape_scratch) + + ! ######################################################################################################################## + ! Eq. (8): W_mbej = + t_jf - t_nb - (1/2 t_jnfb + t_jf t_nb) + ! ######################################################################################################################## + ! + t_jf + allocate(scratch, mold=W_ovvo) + call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvv,t1,scratch) + W_ovvo = cc_int%ovvo + scratch + !$omp parallel default(none) & !$omp private(m, n, i, j, e, f, b, a) & !$omp shared(sys, cc_int, cc_amp) - ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed - ! by a simple dgemm call - !$omp do schedule(static, 10) collapse(4) - do n = 1, nocc - do m = 1, nocc - do j = 1, nocc - do i = 1, nocc - do e = 1, nvirt - W_oooo(i,j,m,n) = W_oooo(i,j,m,n) + t1(j,e)*cc_int%oovo(n,m,e,i) - t1(i,e)*cc_int%oovo(n,m,e,j) - do f = 1, nvirt - W_oooo(i,j,m,n) = W_oooo(i,j,m,n) - 0.5*t2(j,i,f,e)*cc_int%oovv(m,n,f,e) - end do - end do - end do - end do - end do - end do - !$omp end do - - ! [TODO]: make a switch to on-the-fly W_vvvv computation, for when memory is limited - ! Similarly, we order it (e,f,a,b) for the contraction tau_ij^ef W_abef - !$omp do schedule(static, 10) collapse(4) - do b = 1, nvirt - do a = 1, nvirt - do f = 1, nvirt - do e = 1, nvirt - do n = 1, nocc - W_vvvv(e,f,a,b) = W_vvvv(e,f,a,b) + t1(n,b)*cc_int%ovvv(n,a,e,f) - t1(n,a)*cc_int%ovvv(n,b,e,f) - end do - end do - end do - end do - end do - !$omp end do !$omp do schedule(static, 10) collapse(4) do j = 1, nocc do e = 1, nvirt do b = 1, nvirt do m = 1, nocc - do f = 1, nvirt - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - t1(j,f)*cc_int%ovvv(m,b,f,e) - end do - do n = 1, nocc + ! [todo] - for whatever reason this loop is resistant to dgemm W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) + t1(n,b)*cc_int%oovo(n,m,e,j) do f = 1, nvirt W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + t1(n,b)*t1(j,f)) * cc_int%oovv(n,m,f,e) @@ -1075,7 +1081,14 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) tmp_t1 = tmp_t1/D_ia + ! ######################################################################################################################## ! Update T2 + ! Eq. (2) D_ijab t_ijab = + P_ab(t_ijae (F_be - 1/2 t_mb F_me)) - P_(ij)(t_imab (F_mj + 1/2 t_je F_me)) + ! + 1/2 tau_mnab W_mnij + 1/2 tau_ijef W_abef + P_(ij)P_(ab)(t_imae W_mbej - t_ie t_ma ) + ! + P_(ij)(t_ie) - P_(ab)(t_ma ) + ! ######################################################################################################################## + ! + tmp_t2 = cc_int%oovv !$omp parallel default(none) & !$omp shared(sys, cc_amp, int_store, cc_int) @@ -1084,17 +1097,13 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) do a = 1, nvirt do j = 1, nocc do i = 1, nocc - tmp_t2(i,j,a,b) = cc_int%oovv(i,j,a,b) do e = 1, nvirt - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(j,i,e,b)*F_vv(a,e) & - - t1(i,e)*cc_int%ovvv(j,e,a,b) + t1(j,e)*cc_int%ovvv(i,e,a,b) do m = 1, nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*F_ov(m,e)*t2(i,j,b,e)*t1(m,a) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*F_ov(m,e)*(t2(i,j,b,e)*t1(m,a)-t2(i,j,a,e)*t1(m,b)) end do end do do m = 1, nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(m,i,b,a)*F_oo(m,j) + t2(m,j,b,a)*F_oo(m,i) & - - t1(m,a)*cc_int%ovoo(m,b,i,j) + t1(m,b)*cc_int%ovoo(m,a,i,j) + tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(m,i,b,a)*F_oo(m,j) + t2(m,j,b,a)*F_oo(m,i) do e = 1, nvirt tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*t1(j,e)-& t2(j,m,a,b)*t1(i,e)) @@ -1117,11 +1126,21 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) !$omp end do !$omp end parallel - allocate(tmp_t2_s, source=t2) + allocate(tmp_t2_s, reshape_tmp, source=t2) - ! t_ij^ae F_be - call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,(F_vv-matmul(transpose(t1),F_ov)/2),tmp_t2_s) - tmp_t2 = tmp_t2 + tmp_t2_s + ! P_(ab)(t_ijae (F_be - 1/2 t_mb F_me)) + call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,F_vv,tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) + tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + ! P_(ij)(t_ie) = P_(ij)(t_ie) + call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nvirt,t1,cc_int%vovv,tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) + tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + ! @@@ -P_(ab)(t_ma ) = +P_(ab)( t_ma) + ! [todo]: explain the signs! + call dgemm_wrapper('N','N',nocc**2*nvirt,nvirt,nocc,cc_int%oovo,t1,tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) + tmp_t2 = tmp_t2 - tmp_t2_s + reshape_tmp call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2_s) From 95cd3ad8d355ac731532374da28e9de9637b6b50 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Thu, 27 Jan 2022 10:29:38 +0000 Subject: [PATCH 61/71] T2 update optimisation done --- src/ccsd.f90 | 107 +++++++++++++++++++++++++++------------------------ 1 file changed, 56 insertions(+), 51 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index c7fbe6d..c574abe 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -975,41 +975,26 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) tmp_t1 = tmp_t1/D_ia - ! ######################################################################################################################## + ! ######################################################################################################################### ! Update T2 ! Eq. (2) D_ijab t_ijab = + P_ab(t_ijae (F_be - 1/2 t_mb F_me)) - P_(ij)(t_imab (F_mj + 1/2 t_je F_me)) ! + 1/2 tau_mnab W_mnij + 1/2 tau_ijef W_abef + P_(ij)P_(ab)(t_imae W_mbej - t_ie t_ma ) ! + P_(ij)(t_ie) - P_(ab)(t_ma ) - ! ######################################################################################################################## + ! ######################################################################################################################### ! tmp_t2 = cc_int%oovv + allocate(tmp_t2_s, reshape_tmp, mold=t2) !$omp parallel default(none) & - !$omp shared(sys, cc_amp, int_store, cc_int) + !$omp shared(sys, cc_amp, int_store, cc_int, tmp_t2_s) !$omp do schedule(static, 10) collapse(4) do b = 1, nvirt do a = 1, nvirt do j = 1, nocc do i = 1, nocc + tmp_t2_s(i,j,a,b) = sum(t2(:,i,:,a)*W_ovvo(:,b,:,j)) do m = 1, nocc - ! [todo]: this can be cast into dgemm form - ! -P_(ij)(t_imab F_mj) - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(m,i,b,a)*F_oo(m,j) + t2(m,j,b,a)*F_oo(m,i) do e = 1, nvirt - ! -1/2 P_(ij)(t_je F_me t_imab) - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*t1(j,e)-& - t2(j,m,a,b)*t1(i,e)) - end do - end do - - do e = 1, nvirt - do m = 1, nocc - ! P_(ij)P_(ab)(t_imae W_mbej - t_ie t_ma ) - ! [todo]: Maybe one of the permutations is good for dgemm, then the rest can be reshaped? - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & - + t2(m,i,e,a)*W_ovvo(m,b,e,j) - t1(i,e)*t1(m,a)*cc_int%ovvo(m,b,e,j)& - - t2(m,j,e,a)*W_ovvo(m,b,e,i) + t1(j,e)*t1(m,a)*cc_int%ovvo(m,b,e,i)& - - t2(m,i,e,b)*W_ovvo(m,a,e,j) + t1(i,e)*t1(m,b)*cc_int%ovvo(m,a,e,j)& - + t2(m,j,e,b)*W_ovvo(m,a,e,i) - t1(j,e)*t1(m,b)*cc_int%ovvo(m,a,e,i) + tmp_t2_s(i,j,a,b) = tmp_t2_s(i,j,a,b) - t1(i,e)*t1(m,a)*cc_int%ovvo(m,b,e,j) end do end do end do @@ -1018,20 +1003,38 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do !$omp end do !$omp end parallel + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) + tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) + tmp_t2 = tmp_t2 - reshape_tmp + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,4,3/)) + tmp_t2 = tmp_t2 + reshape_tmp - ! P_(ab)(t_ijae (F_be - 1/2 t_mb F_me)) - allocate(tmp_t2_s, reshape_tmp, source=t2) - call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,(F_vv-0.5*matmul(transpose(t1),F_ov)),tmp_t2_s) + ! P_(ab)(t_ijae F_be) + call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,F_vv,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + ! -1/2 P_(ab)(t_ijae t_mb F_me) + call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,matmul(transpose(t1),F_ov),tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) + tmp_t2 = tmp_t2 - (tmp_t2_s - reshape_tmp)/2 + ! -1/2 P_(ij)(t_je F_me t_imab) + call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nocc,matmul(t1,transpose(F_ov)),t2,tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) + tmp_t2 = tmp_t2 - (tmp_t2_s - reshape_tmp)/2 ! P_(ij)(t_ie) = P_(ij)(t_ie) call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nvirt,t1,cc_int%vovv,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp ! @@@ -P_(ab)(t_ma ) = +P_(ab)( t_ma) + ! [todo]: explain the signs! call dgemm_wrapper('N','N',nocc**2*nvirt,nvirt,nocc,cc_int%oovo,t1,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) - tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + tmp_t2 = tmp_t2 - tmp_t2_s + reshape_tmp + ! -P_(ij)(t_imab F_mj) + call dgemm_wrapper('T','N',nocc,nocc*nvirt**2,nocc,F_oo,t2,tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) + tmp_t2 = tmp_t2 - tmp_t2_s + reshape_tmp ! + 1/2 tau_mnab W_mnij, but remember out W_mnij is reshaped as W_ijmn call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 @@ -1081,42 +1084,26 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) tmp_t1 = tmp_t1/D_ia - ! ######################################################################################################################## + ! ######################################################################################################################### ! Update T2 ! Eq. (2) D_ijab t_ijab = + P_ab(t_ijae (F_be - 1/2 t_mb F_me)) - P_(ij)(t_imab (F_mj + 1/2 t_je F_me)) ! + 1/2 tau_mnab W_mnij + 1/2 tau_ijef W_abef + P_(ij)P_(ab)(t_imae W_mbej - t_ie t_ma ) ! + P_(ij)(t_ie) - P_(ab)(t_ma ) - ! ######################################################################################################################## + ! ######################################################################################################################### ! tmp_t2 = cc_int%oovv - + allocate(tmp_t2_s, reshape_tmp, mold=t2) !$omp parallel default(none) & - !$omp shared(sys, cc_amp, int_store, cc_int) + !$omp shared(sys, cc_amp, int_store, cc_int, tmp_t2_s) !$omp do schedule(static, 10) collapse(4) do b = 1, nvirt do a = 1, nvirt do j = 1, nocc do i = 1, nocc - do e = 1, nvirt - do m = 1, nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) + 0.5*F_ov(m,e)*(t2(i,j,b,e)*t1(m,a)-t2(i,j,a,e)*t1(m,b)) - end do - end do - do m = 1, nocc - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - t2(m,i,b,a)*F_oo(m,j) + t2(m,j,b,a)*F_oo(m,i) - do e = 1, nvirt - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) - 0.5*F_ov(m,e)*(t2(i,m,a,b)*t1(j,e)-& - t2(j,m,a,b)*t1(i,e)) - end do - end do - + tmp_t2_s(i,j,a,b) = sum(t2(:,i,:,a)*W_ovvo(:,b,:,j)) do m = 1, nocc do e = 1, nvirt - tmp_t2(i,j,a,b) = tmp_t2(i,j,a,b) & - + t2(m,i,e,a)*W_ovvo(m,b,e,j) - tmp_t1(i,e)*tmp_t1(m,a)*cc_int%ovvo(m,b,e,j)& - - t2(m,j,e,a)*W_ovvo(m,b,e,i) + tmp_t1(j,e)*tmp_t1(m,a)*cc_int%ovvo(m,b,e,i)& - - t2(m,i,e,b)*W_ovvo(m,a,e,j) + tmp_t1(i,e)*tmp_t1(m,b)*cc_int%ovvo(m,a,e,j)& - + t2(m,j,e,b)*W_ovvo(m,a,e,i) - tmp_t1(j,e)*tmp_t1(m,b)*cc_int%ovvo(m,a,e,i) + tmp_t2_s(i,j,a,b) = tmp_t2_s(i,j,a,b) - t1(i,e)*t1(m,a)*cc_int%ovvo(m,b,e,j) end do end do end do @@ -1125,13 +1112,25 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) end do !$omp end do !$omp end parallel + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) + tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) + tmp_t2 = tmp_t2 - reshape_tmp + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,4,3/)) + tmp_t2 = tmp_t2 + reshape_tmp - allocate(tmp_t2_s, reshape_tmp, source=t2) - - ! P_(ab)(t_ijae (F_be - 1/2 t_mb F_me)) + ! P_(ab)(t_ijae F_be) call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,F_vv,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp + ! -1/2 P_(ab)(t_ijae t_mb F_me) + call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,matmul(transpose(t1),F_ov),tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) + tmp_t2 = tmp_t2 - (tmp_t2_s - reshape_tmp)/2 + ! -1/2 P_(ij)(t_je F_me t_imab) + call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nocc,matmul(t1,transpose(F_ov)),t2,tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) + tmp_t2 = tmp_t2 - (tmp_t2_s - reshape_tmp)/2 ! P_(ij)(t_ie) = P_(ij)(t_ie) call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nvirt,t1,cc_int%vovv,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) @@ -1141,11 +1140,17 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) call dgemm_wrapper('N','N',nocc**2*nvirt,nvirt,nocc,cc_int%oovo,t1,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) tmp_t2 = tmp_t2 - tmp_t2_s + reshape_tmp + ! -P_(ij)(t_imab F_mj) + call dgemm_wrapper('T','N',nocc,nocc*nvirt**2,nocc,F_oo,t2,tmp_t2_s) + reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) + tmp_t2 = tmp_t2 - tmp_t2_s + reshape_tmp + ! + 1/2 tau_mnab W_mnij, but remember out W_mnij is reshaped as W_ijmn call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 + ! + 1/2 tau_ijef W_abef call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2_s) tmp_t2 = tmp_t2 + tmp_t2_s/2 - deallocate(tmp_t2_s) + deallocate(tmp_t2_s, reshape_tmp) t1 = tmp_t1 t2 = tmp_t2/D_ijab From 048c0a8d50c477b728b0cba8a314a9fbfa458211 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Thu, 27 Jan 2022 11:07:40 +0000 Subject: [PATCH 62/71] T1 optimisation done --- src/ccsd.f90 | 43 ++++--------------------------------------- 1 file changed, 4 insertions(+), 39 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index c574abe..e2f1320 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -941,33 +941,12 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) !$omp parallel default(none) & !$omp shared(sys, cc_amp, int_store, cc_int) - - ! Implied barrier here, better than master which doesn't have implied barrier ! tmp_t1 can be shared as each loop iteration will update a unique element of it. - !$omp do schedule(static, 10) collapse(2) do a = 1, nvirt do i = 1, nocc - do m = 1, nocc - do e = 1, nvirt - ! #### t_imae F_me - tmp_t1(i,a) = tmp_t1(i,a) + t2(m,i,e,a)*F_ov(m,e) - do f = 1, nvirt - ! #### -1/2 t_imef - tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(m,i,f,e)*cc_int%ovvv(m,a,e,f) - end do - do n = 1, nocc - ! #### -1/2 t_mnae - tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(n,m,e,a)*cc_int%oovo(n,m,e,i) - end do - end do - end do - do e = 1, nvirt - do n = 1, nocc - ! #### -t_nf - tmp_t1(i,a) = tmp_t1(i,a) + t1(n,e)*cc_int%ovvo(n,a,e,i) - end do - end do + tmp_t1(i,a) = tmp_t1(i,a) + sum(t1(:,:)*cc_int%ovvo(:,a,:,i)) + sum(t2(:,i,:,a)*F_ov(:,:)) & + + 0.5*(sum(t2(:,i,:,:)*cc_int%ovvv(:,a,:,:)) - sum(t2(:,:,:,a)*cc_int%oovo(:,:,:,i))) end do end do !$omp end do @@ -1061,22 +1040,8 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) !$omp do schedule(static, 10) collapse(2) do a = 1, nvirt do i = 1, nocc - do m = 1, nocc - do e = 1, nvirt - tmp_t1(i,a) = tmp_t1(i,a) + t2(m,i,e,a)*F_ov(m,e) - do f = 1, nvirt - tmp_t1(i,a) = tmp_t1(i,a) + 0.5*t2(m,i,f,e)*cc_int%ovvv(m,a,f,e) - end do - do n = 1, nocc - tmp_t1(i,a) = tmp_t1(i,a) - 0.5*t2(n,m,e,a)*cc_int%oovo(n,m,e,i) - end do - end do - end do - do e = 1, nvirt - do n = 1, nocc - tmp_t1(i,a) = tmp_t1(i,a) + t1(n,e)*cc_int%ovvo(n,a,e,i) - end do - end do + tmp_t1(i,a) = tmp_t1(i,a) + sum(t1(:,:)*cc_int%ovvo(:,a,:,i)) + sum(t2(:,i,:,a)*F_ov(:,:)) & + + 0.5*(sum(t2(:,i,:,:)*cc_int%ovvv(:,a,:,:)) - sum(t2(:,:,:,a)*cc_int%oovo(:,:,:,i))) end do end do !$omp end do From d78a92e38d6f4a96dd251c8c7547b09517024cab Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Thu, 27 Jan 2022 11:22:33 +0000 Subject: [PATCH 63/71] Final touches, last commit with AB testing blocks --- src/ccsd.f90 | 29 ++++++++++++++++------------- 1 file changed, 16 insertions(+), 13 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index e2f1320..b79081e 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -752,7 +752,7 @@ subroutine build_W(sys, cc_int, cc_amp) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, nvirt=>sys%nvirt, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab,& W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau, W_vvvv=>cc_int%W_vvvv) - if (.false.) then + if (.true.) then ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed ! by a simple dgemm call allocate(scratch,reshape_scratch, mold=W_oooo) @@ -782,10 +782,11 @@ subroutine build_W(sys, cc_int, cc_amp) ! Eq. (7): W_abef = - P_(ab)(t_mb) ! ######################################################################################################################## ! @@@ - P_(ab) t_m^b = + P_(ab) (t_b^m)^T + ! [todo]: explain the signs!! allocate(scratch,reshape_scratch, mold=W_vvvv) call dgemm_wrapper('T','N',nvirt,nvirt**3,nocc,t1,cc_int%ovvv,scratch) reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) - W_vvvv = cc_int%vvvv + scratch - reshape_scratch + W_vvvv = cc_int%vvvv - scratch + reshape_scratch ! We reshape it to W_efab to make contractions more amenable to dgemm reshape_scratch = reshape(W_vvvv,shape(reshape_scratch),order=(/3,4,1,2/)) @@ -796,15 +797,15 @@ subroutine build_W(sys, cc_int, cc_amp) ! Eq. (8): W_mbej = + t_jf - t_nb - (1/2 t_jnfb + t_jf t_nb) ! ######################################################################################################################## ! + t_jf - allocate(scratch, mold=W_ovvo) + allocate(scratch, reshape_scratch, mold=W_ovvo) call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvv,t1,scratch) W_ovvo = cc_int%ovvo + scratch ! @@@ - t_nb = +(t_bn)^T call dgemm_wrapper('T','N',nvirt,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) - W_ovvo = W_ovvo + scratch - deallocate(scratch) - + reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) + W_ovvo = W_ovvo + reshape_scratch + deallocate(scratch, reshape_scratch) ! - (1/2 t_jnfb + t_jf t_nb) !$omp parallel default(none) & @@ -864,29 +865,31 @@ subroutine build_W(sys, cc_int, cc_amp) ! We reshape it to W_efab to make contractions more amenable to dgemm reshape_scratch = reshape(W_vvvv,shape(reshape_scratch),order=(/3,4,1,2/)) W_vvvv = reshape_scratch - deallocate(scratch,reshape_scratch) + deallocate(scratch, reshape_scratch) ! ######################################################################################################################## ! Eq. (8): W_mbej = + t_jf - t_nb - (1/2 t_jnfb + t_jf t_nb) ! ######################################################################################################################## ! + t_jf - allocate(scratch, mold=W_ovvo) + allocate(scratch, reshape_scratch, mold=W_ovvo) call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvv,t1,scratch) W_ovvo = cc_int%ovvo + scratch + ! @@@ - t_nb = +(t_bn)^T + call dgemm_wrapper('T','N',nvirt,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) + reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) + W_ovvo = W_ovvo + reshape_scratch + deallocate(scratch, reshape_scratch) + !$omp parallel default(none) & !$omp private(m, n, i, j, e, f, b, a) & !$omp shared(sys, cc_int, cc_amp) - - !$omp do schedule(static, 10) collapse(4) do j = 1, nocc do e = 1, nvirt do b = 1, nvirt do m = 1, nocc do n = 1, nocc - ! [todo] - for whatever reason this loop is resistant to dgemm - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) + t1(n,b)*cc_int%oovo(n,m,e,j) do f = 1, nvirt W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + t1(n,b)*t1(j,f)) * cc_int%oovv(n,m,f,e) end do @@ -928,7 +931,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nvirt=>sys%nvirt,& W_vvvv=>cc_int%W_vvvv) - if (.false.) then + if (.true.) then ! ######################################################################################################################## ! Update T1 ! Eq. (1) D_ia t_i^a = t_ie F_ae - t_ma F_mi + t_imae F_me - t_nf -1/2 t_imef - 1/2 t_mnae From 48e5639dcad07582e9192fe4dc772a3dd47178a0 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Thu, 27 Jan 2022 11:38:40 +0000 Subject: [PATCH 64/71] Spinorbital CCSD done --- src/ccsd.f90 | 238 ++++++--------------------------------------------- 1 file changed, 26 insertions(+), 212 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index b79081e..7404d8e 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -41,7 +41,6 @@ module ccsd ! In more detail, as e_i = T_i+1 - T_i, and we overwrite T1 when T8 is the newest T matrix, we must make sure we never ! subtract the newest T matrix with the oldest T matrix, and since doing that is tricky in a loop we keep the idx lookup array - ! [TODO]: kick the slowest index to the last! logical :: use_diis = .true. integer :: n_errmat = 8 integer :: n_active = 0 @@ -57,8 +56,8 @@ module ccsd contains subroutine do_ccsd_spinorb(sys, int_store) - ! This is the spinorbital formulation of J.F. Stanton, J. Gauss, J.D. Watts, and R.J. Bartlett, J. Chem. Phys. volume 94, pp. 4334-4345 (1991) (https://doi.org/10.1063/1.460620) - ! [TODO]: closed-shell (spatial) formulation of Hirata, S.; Podeszwa, R.; Tobita, M.; Bartlett, R. J. J. Chem. Phys. 2004, 120 (6), 2581 (https://doi.org/10.1063/1.1637577) + ! This is the spinorbital formulation of J.F. Stanton, J. Gauss, J.D. Watts, and R.J. Bartlett, + ! J. Chem. Phys. volume 94, pp. 4334-4345 (1991) (https://doi.org/10.1063/1.460620) use integrals, only: int_store_t, eri_ind use error_handling, only: error, check_allocate @@ -97,7 +96,6 @@ subroutine do_ccsd_spinorb(sys, int_store) call check_allocate('int_store%asym_spinorb', sys%nbasis**4*16, ierr) associate(n=>sys%nbasis, asym=>int_store%asym_spinorb, eri=>int_store%eri_mo) - ! [TODO]: this isn't necessary but easier for debugging, change to spin lookup arrays or something similar do p = 1, n pa = 2*p-1 pb = pa+1 @@ -686,33 +684,20 @@ subroutine build_F(sys, cc_int, cc_amp) !$omp private(a, e, f, m, n, i) & !$omp shared(sys, cc_int, cc_amp) - ! F_ae = \sum_{mf} t_m^f * - 0.5 \sum_{mnf} \tau~_{mn}^{af} + ! F_ae = t_m^f * - 0.5 tau~_{mn}^{af} !$omp do schedule(static, 10) collapse(2) do a = 1, nvirt do e = 1, nvirt - do m = 1, nocc - do f = 1, nvirt - F_vv(a,e) = F_vv(a,e) + t_ia(m,f) * cc_int%ovvv(m,a,f,e) - do n = 1, nocc - F_vv(a,e) = F_vv(a,e) + 0.5*tau_tilde(n,m,f,a)*cc_int%oovv(n,m,e,f) - end do - end do - end do + F_vv(a,e) = F_vv(a,e) + sum(t_ia(:,:)*cc_int%ovvv(:,a,:,e)) + 0.5*sum(tau_tilde(:,:,:,a)*cc_int%oovv(:,:,e,:)) end do end do !$omp end do - ! F_mi = \sum_{en} t_n^e + 0.5 \sum_{nef} \tau~_{in}^{ef} + ! F_mi = t_n^e + 0.5 tau~_{in}^{ef} !$omp do schedule(static, 10) collapse(2) do m = 1, nocc do i = 1, nocc - do e = 1, nvirt - do n = 1, nocc - ! [todo] - This is terrible cache-wise, but does it warrant creating a new slice/doing a reshape? - F_oo(m,i) = F_oo(m,i) + 0.5*dot_product(tau_tilde(n,i,:,e),cc_int%oovv(m,n,e,:)) & - - t_ia(n,e)*cc_int%ooov(n,m,i,e) - end do - end do + F_oo(m,i) = F_oo(m,i) + 0.5*sum(tau_tilde(i,:,:,:)*cc_int%oovv(m,:,:,:)) - sum(t_ia(:,:)*cc_int%ooov(:,m,i,:)) end do end do !$omp end do @@ -721,7 +706,6 @@ subroutine build_F(sys, cc_int, cc_amp) !$omp do schedule(static, 10) collapse(2) do e = 1, nvirt do m = 1, nocc - ! [todo] - same as above, also investigate if sum(A*B) is better in cases of missed cache F_ov(m,e) = F_ov(m,e) + sum(t_ia(:,:)*cc_int%oovv(m,:,e,:)) end do end do @@ -752,13 +736,12 @@ subroutine build_W(sys, cc_int, cc_amp) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, nvirt=>sys%nvirt, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab,& W_oooo=>cc_int%W_oooo, W_ovvo=>cc_int%W_ovvo, tau=>cc_int%tau, W_vvvv=>cc_int%W_vvvv) - if (.true.) then ! Instead of laying it out like (m,n,i,j) we use (i,j,m,n) because then the contraction tau_mn^ab W_mnij can be processed ! by a simple dgemm call allocate(scratch,reshape_scratch, mold=W_oooo) - ! ######################################################################################################################## + ! ######################################################################################################################### ! Eq. (6): W_mnij = + P_(ij) t_j^e + 1/2 tau_ij^ef - ! ######################################################################################################################## + ! ######################################################################################################################### ! + P_(ij) t_j^e call dgemm_wrapper('N','T',nocc**3,nocc,nvirt,cc_int%ooov,t1,scratch) reshape_scratch = reshape(scratch, shape(reshape_scratch), order=(/1,2,4,3/)) @@ -778,31 +761,32 @@ subroutine build_W(sys, cc_int, cc_amp) W_oooo = reshape_scratch deallocate(scratch,reshape_scratch) - ! ######################################################################################################################## + ! ######################################################################################################################### ! Eq. (7): W_abef = - P_(ab)(t_mb) - ! ######################################################################################################################## - ! @@@ - P_(ab) t_m^b = + P_(ab) (t_b^m)^T - ! [todo]: explain the signs!! + ! ######################################################################################################################### + ! - P_(ab) t_m^b = + P_(ab) (t_b^m)^T allocate(scratch,reshape_scratch, mold=W_vvvv) call dgemm_wrapper('T','N',nvirt,nvirt**3,nocc,t1,cc_int%ovvv,scratch) reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) - W_vvvv = cc_int%vvvv - scratch + reshape_scratch + ! The reshaped tensor is the unpermuted one! + W_vvvv = cc_int%vvvv + reshape_scratch - scratch ! We reshape it to W_efab to make contractions more amenable to dgemm reshape_scratch = reshape(W_vvvv,shape(reshape_scratch),order=(/3,4,1,2/)) W_vvvv = reshape_scratch deallocate(scratch,reshape_scratch) - ! ######################################################################################################################## + ! ######################################################################################################################### ! Eq. (8): W_mbej = + t_jf - t_nb - (1/2 t_jnfb + t_jf t_nb) - ! ######################################################################################################################## + ! ######################################################################################################################### ! + t_jf allocate(scratch, reshape_scratch, mold=W_ovvo) call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvv,t1,scratch) W_ovvo = cc_int%ovvo + scratch - ! @@@ - t_nb = +(t_bn)^T + ! - t_nb = +(t_bn)^T call dgemm_wrapper('T','N',nvirt,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) + ! We need to reshape it because currently the scratch tensor is b,m,e,j reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) W_ovvo = W_ovvo + reshape_scratch deallocate(scratch, reshape_scratch) @@ -817,7 +801,8 @@ subroutine build_W(sys, cc_int, cc_amp) do m = 1, nocc do n = 1, nocc do f = 1, nvirt - ! [todo]: bad cache behaviour (last term), however dgemm isn't that much better herem since two reshapes needed. + ! [todo]: bad cache behaviour (last term), + ! however dgemm isn't that much better here since two reshapes needed. W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + t1(n,b)*t1(j,f)) * cc_int%oovv(m,n,e,f) end do end do @@ -828,80 +813,6 @@ subroutine build_W(sys, cc_int, cc_amp) !$omp end do !$omp end parallel - else - - allocate(scratch,reshape_scratch, mold=W_oooo) - ! ######################################################################################################################## - ! Eq. (6): W_mnij = + P_(ij) t_j^e + 1/2 tau_ij^ef - ! ######################################################################################################################## - ! + P_(ij) t_j^e - call dgemm_wrapper('N','T',nocc**3,nocc,nvirt,cc_int%ooov,t1,scratch) - reshape_scratch = reshape(scratch, shape(reshape_scratch), order=(/1,2,4,3/)) - W_oooo = cc_int%oooo + scratch - reshape_scratch - deallocate(reshape_scratch) - - ! 1/2 tau_ijef - allocate(reshape_scratch(nvirt,nvirt,nocc,nocc)) - reshape_scratch = reshape(tau, shape(reshape_scratch), order=(/3,4,1,2/)) - call dgemm_wrapper('N','N',nocc**2,nocc**2,nvirt**2,cc_int%oovv,reshape_scratch,scratch) - W_oooo = W_oooo + scratch/2 - deallocate(reshape_scratch) - - ! We reshape it to W_ijmn to make contractions more amenable to dgemm - allocate(reshape_scratch, mold=W_oooo) - reshape_scratch = reshape(W_oooo, shape(reshape_scratch), order=(/3,4,1,2/)) - W_oooo = reshape_scratch - deallocate(scratch,reshape_scratch) - - ! ######################################################################################################################## - ! Eq. (7): W_abef = - P_(ab)(t_mb) - ! ######################################################################################################################## - ! [todo]: explain the signs!! - allocate(scratch,reshape_scratch, mold=W_vvvv) - call dgemm_wrapper('T','N',nvirt,nvirt**3,nocc,t1,cc_int%ovvv,scratch) - reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) - W_vvvv = cc_int%vvvv - scratch + reshape_scratch - - ! We reshape it to W_efab to make contractions more amenable to dgemm - reshape_scratch = reshape(W_vvvv,shape(reshape_scratch),order=(/3,4,1,2/)) - W_vvvv = reshape_scratch - deallocate(scratch, reshape_scratch) - - ! ######################################################################################################################## - ! Eq. (8): W_mbej = + t_jf - t_nb - (1/2 t_jnfb + t_jf t_nb) - ! ######################################################################################################################## - ! + t_jf - allocate(scratch, reshape_scratch, mold=W_ovvo) - call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvv,t1,scratch) - W_ovvo = cc_int%ovvo + scratch - - ! @@@ - t_nb = +(t_bn)^T - call dgemm_wrapper('T','N',nvirt,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) - reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) - W_ovvo = W_ovvo + reshape_scratch - deallocate(scratch, reshape_scratch) - - !$omp parallel default(none) & - !$omp private(m, n, i, j, e, f, b, a) & - !$omp shared(sys, cc_int, cc_amp) - !$omp do schedule(static, 10) collapse(4) - do j = 1, nocc - do e = 1, nvirt - do b = 1, nvirt - do m = 1, nocc - do n = 1, nocc - do f = 1, nvirt - W_ovvo(m,b,e,j) = W_ovvo(m,b,e,j) - (0.5*t2(j,n,f,b) + t1(n,b)*t1(j,f)) * cc_int%oovv(n,m,f,e) - end do - end do - end do - end do - end do - end do - !$omp end do - !$omp end parallel - end if - end associate end subroutine build_W @@ -931,11 +842,10 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) W_ovvo=>cc_int%W_ovvo,tau=>cc_int%tau,tau_tilde=>cc_int%tau_tilde,nocc=>sys%nocc,nvirt=>sys%nvirt,& W_vvvv=>cc_int%W_vvvv) - if (.true.) then - ! ######################################################################################################################## + ! ######################################################################################################################### ! Update T1 ! Eq. (1) D_ia t_i^a = t_ie F_ae - t_ma F_mi + t_imae F_me - t_nf -1/2 t_imef - 1/2 t_mnae - ! ######################################################################################################################## + ! ######################################################################################################################### ! #### t_ie F_ae tmp_t1 = matmul(t1,transpose(F_vv)) @@ -948,6 +858,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) !$omp do schedule(static, 10) collapse(2) do a = 1, nvirt do i = 1, nocc + ! We can't do sum(A + B) because the order of (i,a) doesn't generally match between these tmp_t1(i,a) = tmp_t1(i,a) + sum(t1(:,:)*cc_int%ovvo(:,a,:,i)) + sum(t2(:,i,:,a)*F_ov(:,:)) & + 0.5*(sum(t2(:,i,:,:)*cc_int%ovvv(:,a,:,:)) - sum(t2(:,:,:,a)*cc_int%oovo(:,:,:,i))) end do @@ -1008,106 +919,11 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nvirt,t1,cc_int%vovv,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp - ! @@@ -P_(ab)(t_ma ) = +P_(ab)( t_ma) - ! [todo]: explain the signs! - call dgemm_wrapper('N','N',nocc**2*nvirt,nvirt,nocc,cc_int%oovo,t1,tmp_t2_s) - reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) - tmp_t2 = tmp_t2 - tmp_t2_s + reshape_tmp - ! -P_(ij)(t_imab F_mj) - call dgemm_wrapper('T','N',nocc,nocc*nvirt**2,nocc,F_oo,t2,tmp_t2_s) - reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) - tmp_t2 = tmp_t2 - tmp_t2_s + reshape_tmp - ! + 1/2 tau_mnab W_mnij, but remember out W_mnij is reshaped as W_ijmn - call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2_s) - tmp_t2 = tmp_t2 + tmp_t2_s/2 - ! + 1/2 tau_ijef W_abef - call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2_s) - tmp_t2 = tmp_t2 + tmp_t2_s/2 - deallocate(tmp_t2_s, reshape_tmp) - - t1 = tmp_t1 - t2 = tmp_t2/D_ijab - - else - ! Update T1 - - tmp_t1 = matmul(t1,transpose(F_vv)) - tmp_t1 = tmp_t1 - matmul(transpose(F_oo),t1) - - !$omp parallel default(none) & - !$omp shared(sys, cc_amp, int_store, cc_int) - - ! Implied barrier here, better than master which doesn't have implied barrier - ! tmp_t1 can be shared as each loop iteration will update a unique element of it. - - !$omp do schedule(static, 10) collapse(2) - do a = 1, nvirt - do i = 1, nocc - tmp_t1(i,a) = tmp_t1(i,a) + sum(t1(:,:)*cc_int%ovvo(:,a,:,i)) + sum(t2(:,i,:,a)*F_ov(:,:)) & - + 0.5*(sum(t2(:,i,:,:)*cc_int%ovvv(:,a,:,:)) - sum(t2(:,:,:,a)*cc_int%oovo(:,:,:,i))) - end do - end do - !$omp end do - !$omp end parallel - - tmp_t1 = tmp_t1/D_ia - - ! ######################################################################################################################### - ! Update T2 - ! Eq. (2) D_ijab t_ijab = + P_ab(t_ijae (F_be - 1/2 t_mb F_me)) - P_(ij)(t_imab (F_mj + 1/2 t_je F_me)) - ! + 1/2 tau_mnab W_mnij + 1/2 tau_ijef W_abef + P_(ij)P_(ab)(t_imae W_mbej - t_ie t_ma ) - ! + P_(ij)(t_ie) - P_(ab)(t_ma ) - ! ######################################################################################################################### - ! - tmp_t2 = cc_int%oovv - allocate(tmp_t2_s, reshape_tmp, mold=t2) - !$omp parallel default(none) & - !$omp shared(sys, cc_amp, int_store, cc_int, tmp_t2_s) - !$omp do schedule(static, 10) collapse(4) - do b = 1, nvirt - do a = 1, nvirt - do j = 1, nocc - do i = 1, nocc - tmp_t2_s(i,j,a,b) = sum(t2(:,i,:,a)*W_ovvo(:,b,:,j)) - do m = 1, nocc - do e = 1, nvirt - tmp_t2_s(i,j,a,b) = tmp_t2_s(i,j,a,b) - t1(i,e)*t1(m,a)*cc_int%ovvo(m,b,e,j) - end do - end do - end do - end do - end do - end do - !$omp end do - !$omp end parallel - reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) - tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp - reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) - tmp_t2 = tmp_t2 - reshape_tmp - reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,4,3/)) - tmp_t2 = tmp_t2 + reshape_tmp - - ! P_(ab)(t_ijae F_be) - call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,F_vv,tmp_t2_s) - reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) - tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp - ! -1/2 P_(ab)(t_ijae t_mb F_me) - call dgemm_wrapper('N','T',nocc**2*nvirt,nvirt,nvirt,t2,matmul(transpose(t1),F_ov),tmp_t2_s) - reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) - tmp_t2 = tmp_t2 - (tmp_t2_s - reshape_tmp)/2 - ! -1/2 P_(ij)(t_je F_me t_imab) - call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nocc,matmul(t1,transpose(F_ov)),t2,tmp_t2_s) - reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) - tmp_t2 = tmp_t2 - (tmp_t2_s - reshape_tmp)/2 - ! P_(ij)(t_ie) = P_(ij)(t_ie) - call dgemm_wrapper('N','N',nocc,nocc*nvirt**2,nvirt,t1,cc_int%vovv,tmp_t2_s) - reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) - tmp_t2 = tmp_t2 + tmp_t2_s - reshape_tmp - ! @@@ -P_(ab)(t_ma ) = +P_(ab)( t_ma) - ! [todo]: explain the signs! + ! -P_(ab)(t_ma ) = +P_(ab)( t_ma) call dgemm_wrapper('N','N',nocc**2*nvirt,nvirt,nocc,cc_int%oovo,t1,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/1,2,4,3/)) - tmp_t2 = tmp_t2 - tmp_t2_s + reshape_tmp + ! The reshaped tensor is the unpermuted one, since tmp_t2_s is i,j,b,a + tmp_t2 = tmp_t2 + reshape_tmp - tmp_t2_s ! -P_(ij)(t_imab F_mj) call dgemm_wrapper('T','N',nocc,nocc*nvirt**2,nocc,F_oo,t2,tmp_t2_s) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) @@ -1123,7 +939,6 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) t1 = tmp_t1 t2 = tmp_t2/D_ijab - end if end associate end subroutine update_amplitudes @@ -1159,7 +974,7 @@ subroutine update_cc_energy(sys, st, cc_int, cc_amp, conv) !$omp shared(sys,st,cc_amp,ecc,rmst2,cc_int) ecc = 0.0_p rmst2 = 0.0_p - !$omp do schedule(static, 10) collapse(4) reduction(+:ecc,rmst2) + !$omp do schedule(static, 10) collapse(2) reduction(+:ecc,rmst2) do b = 1, nvirt do a = 1, nvirt do j = 1, nocc @@ -1175,7 +990,6 @@ subroutine update_cc_energy(sys, st, cc_int, cc_amp, conv) !$omp end parallel st%energy = ecc st%t2_old = t2 - ! [TODO]: stop hard-coding tolerance, or at least unify it with HF if (sqrt(rmst2) < sys%ccsd_t_tol .and. abs(st%energy-st%energy_old) < sys%ccsd_e_tol) conv = .true. end associate From 2485b2a5e7fa41b40dcf59cb7ae1cf6db6807885 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Thu, 27 Jan 2022 13:44:38 +0000 Subject: [PATCH 65/71] Clean up unused variables and arguments --- src/ccsd.f90 | 19 ++++++++----------- src/hf.f90 | 19 +++++++------------ src/integrals.f90 | 3 +-- src/main.F90 | 2 +- 4 files changed, 17 insertions(+), 26 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 7404d8e..12706ab 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -65,7 +65,7 @@ subroutine do_ccsd_spinorb(sys, int_store) type(system_t), intent(inout) :: sys type(int_store_t), intent(inout) :: int_store - integer :: i, j, k, a, b, p, q, r, s + integer :: p, q, r, s integer :: pr, qr, pa, pb, qa, qb, ra, rb, sa, sb real(dp) :: prqs, psqr real(dp) :: err @@ -193,7 +193,7 @@ subroutine do_ccsd_spinorb(sys, int_store) ! Initialise intermediate arrays and DIIS data ! ############################################ write(iunit, '(1X, A)') 'Initialise CC intermediate tensors and DIIS auxilliary arrays...' - call init_cc(sys, int_store, cc_amp, cc_int) + call init_cc(sys, cc_amp, cc_int) allocate(st%t2_old, source=cc_amp%t_ijab) call init_diis_cc_t(sys, diis) @@ -254,7 +254,7 @@ subroutine do_ccsd_spatial(sys, int_store) type(system_t), intent(inout) :: sys type(int_store_t), intent(inout) :: int_store - integer :: i, j, a, b, p, q, r, s + integer :: p, q, r, s integer :: pr, qr, pa, pb, qa, qb, ra, rb, sa, sb real(dp) :: prqs, psqr real(dp) :: err @@ -354,7 +354,7 @@ subroutine do_ccsd_spatial(sys, int_store) ! Initialise intermediate arrays and DIIS data ! ############################################ write(iunit, '(1X, A)') 'Initialise CC intermediate tensors and DIIS auxilliary arrays...' - call init_cc(sys, int_store, cc_amp, cc_int) + call init_cc(sys, cc_amp, cc_int) allocate(st%t2_old, source=cc_amp%t_ijab) call init_diis_cc_t(sys, diis) @@ -406,10 +406,8 @@ subroutine do_ccsd_spatial(sys, int_store) end subroutine do_ccsd_spatial - subroutine init_cc(sys, int_store, cc_amp, cc_int) + subroutine init_cc(sys, cc_amp, cc_int) ! Initialise many CC related quantities. - ! In: - ! int_store: int_store_t object holding integrals. ! In/out: ! sys: system under study. ! cc_amp: CC amplitudes @@ -419,11 +417,10 @@ subroutine init_cc(sys, int_store, cc_amp, cc_int) use error_handling, only: check_allocate type(system_t), intent(inout) :: sys - type(int_store_t), intent(in) :: int_store type(cc_amp_t), intent(inout) :: cc_amp type(cc_int_t), intent(inout) :: cc_int - integer :: p, q, r, s, i, j, a, b, ierr + integer :: i, j, a, b, ierr integer, parameter :: iunit = 6 write(iunit, '(1X, A)') 'Forming energy denominator matrices...' @@ -730,7 +727,7 @@ subroutine build_W(sys, cc_int, cc_amp) type(system_t), intent(in) :: sys type(cc_amp_t), intent(in) :: cc_amp type(cc_int_t), intent(inout) :: cc_int - integer :: m, n, i, j, e, f, b, a + integer :: m, n, j, e, f, b real(p), dimension(:,:,:,:), allocatable :: scratch, reshape_scratch associate(nbasis=>sys%nbasis, nocc=>sys%nocc, nvirt=>sys%nvirt, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab,& @@ -835,7 +832,7 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) real(p), dimension(:,:,:,:), allocatable :: tmp_t2_s, reshape_tmp - integer :: i, j, a, b, m, n, e, f + integer :: i, j, a, b, m, e associate(tmp_t1=>cc_int%tmp_tia,tmp_t2=>cc_int%tmp_tijab,t1=>cc_amp%t_ia,t2=>cc_amp%t_ijab,asym=>int_store%asym_spinorb, & F_oo=>cc_int%F_oo,F_ov=>cc_int%F_ov,F_vv=>cc_int%F_vv,D_ia=>cc_int%D_ia,D_ijab=>cc_int%D_ijab,W_oooo=>cc_int%W_oooo, & diff --git a/src/hf.f90 b/src/hf.f90 index 4a78aad..db783ad 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -28,13 +28,10 @@ subroutine do_rhf(sys, int_store) type(mat_t) :: ovlp, fockmat real(p) :: ortmat(sys%nbasis,sys%nbasis) - real(p) :: fock(sys%nbasis,sys%nbasis) - real(p) :: coeff(sys%nbasis,sys%nbasis) real(p) :: density(sys%nbasis,sys%nbasis) - real(p) :: tmpmat(sys%nbasis,sys%nbasis) type(state_t) :: st - integer :: iter, maxiter, iunit, i, j, ierr + integer :: iter, maxiter, iunit, i logical :: conv = .false. type(diis_t) :: diis @@ -143,10 +140,8 @@ subroutine update_diis(diis, fock, density, ovlp) diis%iter = diis%iter+1 if (diis%iter > diis%n_errmat) diis%iter = diis%iter - diis%n_errmat if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 - diis%F(diis%iter,:,:) = 0.0_p - diis%e(diis%iter,:,:) = 0.0_p - diis%F(diis%iter,:,:) = fock(:,:) - diis%e(diis%iter,:,:) = matmul(fock, matmul(density,ovlp)) & + diis%F(:,:,diis%iter) = fock(:,:) + diis%e(:,:,diis%iter) = matmul(fock, matmul(density,ovlp)) & - matmul(ovlp, matmul(density, fock)) associate(n=>diis%n_active, nerr=>diis%n_errmat) @@ -162,14 +157,14 @@ subroutine update_diis(diis, fock, density, ovlp) diis%c = diis%rhs do i = 1, n do j = 1, i - diis%B(i,j) = sum(diis%e(i,:,:)*diis%e(j,:,:)) + diis%B(i,j) = sum(diis%e(:,:,i)*diis%e(:,:,j)) end do end do call linsolve(diis%B, diis%c, ierr) if (ierr /= 0) call error('hf::update_diis', 'Linear solve failed!') fock = 0.0_p do i = 1, n - fock = fock + diis%c(i) * diis%F(i,:,:) + fock = fock + diis%c(i) * diis%F(:,:,i) end do end if end associate @@ -187,8 +182,8 @@ subroutine init_diis_t(sys, diis) diis%use_diis = .false. else associate(n=>sys%nbasis) - allocate(diis%e(diis%n_errmat,n,n), source=0.0_p) - allocate(diis%F(diis%n_errmat,n,n), source=0.0_p) + allocate(diis%e(n,n,diis%n_errmat), source=0.0_p) + allocate(diis%F(n,n,diis%n_errmat), source=0.0_p) end associate end if end subroutine init_diis_t diff --git a/src/integrals.f90 b/src/integrals.f90 index 09e7cc3..86812c2 100644 --- a/src/integrals.f90 +++ b/src/integrals.f90 @@ -42,7 +42,7 @@ subroutine read_integrals_in(sys, int_store) type(system_t), intent(inout) :: sys character(20) :: enuc_f, ovlp_f, ke_f, ele_nuc_f, eri_f - integer :: i, j, iunit, ir, natoms, ios, nbasis + integer :: iunit, ir, ios, nbasis integer :: ibasis, jbasis, abasis, bbasis, ij_ind, ab_ind real(p) :: intgrl @@ -205,7 +205,6 @@ subroutine print_sys_info(sys, int_store) type(int_store_t), intent(in) :: int_store integer :: iunit = 6 - integer :: i write(iunit, '(1X, 20("-"))') write(iunit, '(1X, A)') 'System information' diff --git a/src/main.F90 b/src/main.F90 index 8a74818..554c065 100644 --- a/src/main.F90 +++ b/src/main.F90 @@ -14,7 +14,7 @@ program main type(int_store_t) :: int_store type(system_t) :: sys - integer :: i, iunit + integer :: iunit integer(kind=8) :: t0, t1, count_rate, count_max integer :: date_values(8) From 49f6a51a26a83f9b813b05b8e239792508faee72 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sat, 29 Jan 2022 14:05:37 +0000 Subject: [PATCH 66/71] Working CC DIIS finally, also add options for maxiter --- dat/els.in | 2 + src/ccsd.f90 | 136 +++++++++++++++++++++++++------------------------ src/hf.f90 | 11 ++-- src/system.f90 | 8 ++- 4 files changed, 84 insertions(+), 73 deletions(-) diff --git a/dat/els.in b/dat/els.in index 4c518a4..a4656a4 100644 --- a/dat/els.in +++ b/dat/els.in @@ -6,4 +6,6 @@ scf_diis_n_errmat=6, ccsd_e_tol=1e-6, ccsd_t_tol=1e-7, ccsd_diis_n_errmat=8 +scf_maxiter = 50, +ccsd_maxiter = 50 / diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 12706ab..0043ba2 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -34,23 +34,28 @@ module ccsd ! (https://doi.org/10.1016/0009-2614(86)80461-4) ! These are identical as the HF-SCF ones, other than that we store and use the T matrices, - ! instead of Fock matrices for error matrix computation. Also that we don't store the error matrices as that will - ! double the memory usage in what is a fast step (compared to updating amplitudes) anyway. Instead we use the idx lookup array - ! to make sure we take the right differences in computing e_i matrices on the fly. - ! - ! In more detail, as e_i = T_i+1 - T_i, and we overwrite T1 when T8 is the newest T matrix, we must make sure we never - ! subtract the newest T matrix with the oldest T matrix, and since doing that is tricky in a loop we keep the idx lookup array + ! instead of Fock matrices for error matrix computation. + ! The details of the update is slightly subtle and quite easy to get wrong: + ! Diagrammatically, + ! MP1 amp (T0')-------> T1 ====> T1' + ! amp. eqs. DIIS + ! T1'-------> T2 ====> T2' + ! T2'-------> T3 ====> T3' + ! and so on. + ! The error matrices are defined: e_i = T_i - T_{i-1}' + ! and the linear combination is over the unprimed amplitudes. + ! This means we **have to** store both the unprimed amplitudes and the error matrices, plus two temporary arrays + ! to compute the error matrix at each iteration logical :: use_diis = .true. integer :: n_errmat = 8 integer :: n_active = 0 integer :: iter = 0 - real(p), allocatable :: t1(:,:,:) - real(p), allocatable :: t2(:,:,:,:,:) + real(p), dimension(:,:,:), allocatable :: t1, e1, t1_s(:,:) + real(p), dimension(:,:,:,:,:), allocatable :: t2, e2, t2_s(:,:,:,:) real(p), allocatable :: B(:,:) real(p), allocatable :: c(:) real(p), allocatable :: rhs(:) - integer, allocatable :: idx(:,:) end type diis_cc_t contains @@ -77,7 +82,7 @@ subroutine do_ccsd_spinorb(sys, int_store) type(cc_amp_t) :: cc_amp integer :: ierr, iter integer, parameter :: iunit = 6 - integer, parameter :: maxiter = 100 + integer, parameter :: maxiter = 20 type(cc_int_t) :: cc_int logical :: conv @@ -209,7 +214,13 @@ subroutine do_ccsd_spinorb(sys, int_store) ! Iterative CC solver ! ################### associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) - do iter = 1, maxiter + do iter = 1, sys%ccsd_maxiter + if (diis%use_diis) then + ! These are for computing the error matrices for DIIS procedure + diis%t1_s = cc_amp%t_ia + diis%t2_s = cc_amp%t_ijab + end if + ! Update intermediate tensors call build_tau(sys, cc_amp, cc_int) call build_F(sys, cc_int, cc_amp) @@ -218,10 +229,12 @@ subroutine do_ccsd_spinorb(sys, int_store) ! CC amplitude equations call update_amplitudes(sys, cc_amp, int_store, cc_int) call update_cc_energy(sys, st, cc_int, cc_amp, conv) - + call system_clock(t1) + write(iunit, '(1X, A, 1X, I2, 2X, F15.12, 2X, F8.6, 1X, A)') 'Iteration',iter,st%energy,real(t1-t0, kind=dp)/c_rate,'s' + t0=t1 if (conv) then write(iunit, '(1X, A)') 'Convergence reached within tolerance.' - write(iunit, '(1X, A, 1X, F15.8)') 'Final CCSD Energy (Hartree):', st%energy + write(iunit, '(1X, A, 1X, F15.12)') 'Final CCSD Energy (Hartree):', st%energy ! Copied for return sys%e_ccsd = st%energy @@ -230,10 +243,6 @@ subroutine do_ccsd_spinorb(sys, int_store) exit end if call update_diis_cc(diis, cc_amp) - - call system_clock(t1) - write(iunit, '(1X, A, 1X, I2, 2X, F10.7, 2X, F8.6, 1X, A)') 'Iteration', iter, st%energy,real(t1-t0, kind=dp)/c_rate,'s' - t0=t1 end do end associate @@ -518,15 +527,22 @@ subroutine init_diis_cc_t(sys, diis) ! Switch off diis diis%use_diis = .false. else - allocate(diis%idx(diis%n_errmat-1,2), source=0) - diis%iter = 0; diis%n_active = 0 associate(nvirt=>sys%nvirt, nocc=>sys%nocc) allocate(diis%t1(nocc,nvirt,diis%n_errmat), source=0.0_p, stat=ierr) call check_allocate('diis%t1', diis%n_errmat*nocc*nvirt, ierr) + allocate(diis%e1, source=diis%t1, stat=ierr) + call check_allocate('diis%e1', diis%n_errmat*nocc*nvirt, ierr) + allocate(diis%t1_s(nocc,nvirt), source=0.0_p, stat=ierr) + call check_allocate('diis%t1_s', nocc*nvirt, ierr) + allocate(diis%t2(nocc,nocc,nvirt,nvirt,diis%n_errmat), source=0.0_p, stat=ierr) - call check_allocate('diis%t1', diis%n_errmat*(nocc*nvirt)**2, ierr) + call check_allocate('diis%t2', diis%n_errmat*(nocc*nvirt)**2, ierr) + allocate(diis%e2(nocc,nocc,nvirt,nvirt,diis%n_errmat), source=diis%t2, stat=ierr) + call check_allocate('diis%e2', diis%n_errmat*(nocc*nvirt)**2, ierr) + allocate(diis%t2_s(nocc,nocc,nvirt,nvirt), source=0.0_p, stat=ierr) + call check_allocate('diis%t2_s', diis%n_errmat*(nocc*nvirt)**2, ierr) end associate end if end subroutine init_diis_cc_t @@ -545,65 +561,51 @@ subroutine update_diis_cc(diis, cc_amp) integer :: i, j, ierr + associate(n=>diis%n_active, nerr=>diis%n_errmat, it=>diis%iter) if (diis%use_diis) then - ! Increment counter - diis%iter = diis%iter+1 - ! A modulo behaviour, but makes sure we never get iter = 0 - if (diis%iter > diis%n_errmat) diis%iter = diis%iter - diis%n_errmat - ! In the first few iterations we need to make sure we don't accidentally access the empty arrays - if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 - ! Store the current amplitudes - diis%t1(:,:,diis%iter) = cc_amp%t_ia - diis%t2(:,:,:,:,diis%iter) = cc_amp%t_ijab - - associate(n=>diis%n_active, nerr=>diis%n_errmat, it=>diis%iter, idx=>diis%idx) - if (n > 2) then - ! We need at least three CC iterations to have at least two error matrices - - ! Construct index list (idx), see diis_cc_t documentation for motivation - ! Concrete example, say n_errmat=8, and we're at iteration 4 (overwriting the 4th T matrices), so the error matrices - ! should be: - ! e_1 = T4-T3 (== 4-3), e_2=3-2, e_3=2-1, e_4=1-8, e_5=8-7, e_6=7-6, e_7=6-5 - ! So our idx array should look like - ! 4 3 2 1 8 7 6 - ! 3 2 1 8 7 6 5 - ! (note that the code below gives something like this but with the columns swapped around but that's ok - ! since we don't care about chronological ordering) - do i = 1, n-1 - idx(i,1) = it + 1 - i - if (idx(i,1) < 1) idx(i,1) = idx(i,1) + n - idx(i,2) = it - i - if (idx(i,2) < 1) idx(i,2) = idx(i,2) + n - end do + diis%iter = diis%iter+1 + ! A modulo behaviour, but makes sure we never get iter = 0 + if (diis%iter > diis%n_errmat) diis%iter = diis%iter - diis%n_errmat + + ! In the first few iterations we need to make sure we don't accidentally access the empty arrays + if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 + + ! Store the current amplitudes + diis%t1(:,:,diis%iter) = cc_amp%t_ia + diis%t2(:,:,:,:,diis%iter) = cc_amp%t_ijab + + ! Calculate error matrices for the current iteration + diis%e1(:,:,diis%iter) = cc_amp%t_ia - diis%t1_s + diis%e2(:,:,:,:,diis%iter) = cc_amp%t_ijab - diis%t2_s + ! Construct the B matrix if (n <= nerr) then if (allocated(diis%B)) deallocate(diis%B, diis%c, diis%rhs) - allocate(diis%B(n,n), diis%c(n), diis%rhs(n), source=0.0_p) + allocate(diis%B(n+1,n+1), diis%c(n+1), diis%rhs(n+1), source=0.0_p) end if - diis%B(n,:) = -1.0_p - diis%B(n,n) = 0.0_p - diis%rhs(n) = -1.0_p + diis%B(n+1,:) = -1.0_p + diis%B(n+1,n+1) = 0.0_p + diis%rhs(n+1) = -1.0_p diis%c = diis%rhs - do i = 1, n-1 + do i = 1, n do j = 1, i - ! We compute the error matrices on the fly, linsolve/dsysv only need the upper triangle - diis%B(i,j) = sum((diis%t1(:,:,idx(i,1))-diis%t1(:,:,idx(i,2)))*(diis%t1(:,:,idx(j,1))-diis%t1(:,:,idx(j,2)))) & - + sum((diis%t2(:,:,:,:,idx(i,1))-diis%t2(:,:,:,:,idx(i,2)))*(diis%t2(:,:,:,:,idx(j,1))-diis%t2(:,:,:,:,idx(j,2)))) + ! We compute the error matrices on the fly, linsolve/dsysv only need the lower triangle + ! Because of how the idx array works, c1 corresponds to the weightage of the newest error vector, and so on. + diis%B(i,j) = sum(diis%e1(:,:,i)*diis%e1(:,:,j)) + sum(diis%e2(:,:,:,:,i)*diis%e2(:,:,:,:,j)) end do end do + call linsolve(diis%B, diis%c, ierr) if (ierr /= 0) call error('ccsd::update_diis_cc', 'Linear solve failed!') + cc_amp%t_ia = 0.0_p cc_amp%t_ijab = 0.0_p - do i = 1, n-1 - cc_amp%t_ia = cc_amp%t_ia + diis%c(i) * diis%t1(:,:,idx(i,1)) - cc_amp%t_ijab = cc_amp%t_ijab + diis%c(i) * diis%t2(:,:,:,:,idx(i,1)) + do i = 1, n + cc_amp%t_ia = cc_amp%t_ia + diis%c(i) * diis%t1(:,:,i) + cc_amp%t_ijab = cc_amp%t_ijab + diis%c(i) * diis%t2(:,:,:,:,i) end do end if end associate - else - continue - end if end subroutine update_diis_cc subroutine deallocate_diis_cc_t(diis) @@ -613,7 +615,7 @@ subroutine deallocate_diis_cc_t(diis) type(diis_cc_t), intent(inout) :: diis - deallocate(diis%t1, diis%t2, diis%B, diis%c, diis%rhs) + deallocate(diis%t1, diis%t2, diis%B, diis%c, diis%rhs, diis%e1, diis%e2, diis%t1_s, diis%t2_s) end subroutine deallocate_diis_cc_t subroutine build_tau(sys, cc_amp, cc_int) @@ -966,11 +968,11 @@ subroutine update_cc_energy(sys, st, cc_int, cc_amp, conv) conv = .false. st%energy_old = st%energy associate(nocc=>sys%nocc, nvirt=>sys%nvirt, oovv=>cc_int%oovv, t1=>cc_amp%t_ia, t2=>cc_amp%t_ijab) + ecc = 0.0_p + rmst2 = 0.0_p !$omp parallel default(none) & !$omp private(i,j,a,b) & !$omp shared(sys,st,cc_amp,ecc,rmst2,cc_int) - ecc = 0.0_p - rmst2 = 0.0_p !$omp do schedule(static, 10) collapse(2) reduction(+:ecc,rmst2) do b = 1, nvirt do a = 1, nvirt @@ -1017,10 +1019,10 @@ subroutine do_ccsd_t_spinorb(sys, int_store) associate(nbasis=>sys%nbasis, nocc=>sys%nocc, e=>sys%canon_levels_spinorb, t1=>sys%t1, t2=>sys%t2,& asym=>int_store%asym_spinorb) + e_T = 0.0_p !$omp parallel default(none) & !$omp private(i, j, k, a, b, c, f, m, tmp_t3d, tmp_t3c, tmp_t3c_d, ierr) & !$omp shared(sys, int_store, e_T) - e_T = 0.0_p ! Declare heap-allocated arrays inside parallel region allocate(tmp_t3d(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) diff --git a/src/hf.f90 b/src/hf.f90 index db783ad..2ecff52 100644 --- a/src/hf.f90 +++ b/src/hf.f90 @@ -31,12 +31,11 @@ subroutine do_rhf(sys, int_store) real(p) :: density(sys%nbasis,sys%nbasis) type(state_t) :: st - integer :: iter, maxiter, iunit, i + integer :: iter, iunit, i logical :: conv = .false. type(diis_t) :: diis iunit = 6 - maxiter = 100 write(iunit, '(1X, 23("-"))') write(iunit, '(1X, A)') 'Restricted Hartree-Fock' write(iunit, '(1X, 23("-"))') @@ -76,7 +75,7 @@ subroutine do_rhf(sys, int_store) ! Iterative SCF solver ! #################### - do iter = 1, maxiter + do iter = 1, sys%scf_maxiter ! F' is the fock matrix in orthogonal AO basis, where F is in the original non-orthogonal basis ! F' = X^T F X fockmat%ao_ort = matmul(transpose(ortmat), matmul(fockmat%ao, ortmat)) @@ -137,6 +136,7 @@ subroutine update_diis(diis, fock, density, ovlp) integer :: i, j, ierr + if (diis%use_diis) then diis%iter = diis%iter+1 if (diis%iter > diis%n_errmat) diis%iter = diis%iter - diis%n_errmat if (diis%n_active < diis%n_errmat) diis%n_active = diis%n_active+1 @@ -160,6 +160,8 @@ subroutine update_diis(diis, fock, density, ovlp) diis%B(i,j) = sum(diis%e(:,:,i)*diis%e(:,:,j)) end do end do + do i = 1, n+1 + end do call linsolve(diis%B, diis%c, ierr) if (ierr /= 0) call error('hf::update_diis', 'Linear solve failed!') fock = 0.0_p @@ -168,6 +170,7 @@ subroutine update_diis(diis, fock, density, ovlp) end do end if end associate + end if end subroutine update_diis subroutine init_diis_t(sys, diis) @@ -191,7 +194,7 @@ end subroutine init_diis_t subroutine deallocate_diis_t(diis) type(diis_t), intent(inout) :: diis - deallocate(diis%e, diis%F, diis%B, diis%c, diis%rhs) + if (diis%use_diis) deallocate(diis%e, diis%F, diis%B, diis%c, diis%rhs) end subroutine deallocate_diis_t subroutine diagonalise(mat) diff --git a/src/system.f90 b/src/system.f90 index fcf3bd3..a48ac6d 100644 --- a/src/system.f90 +++ b/src/system.f90 @@ -39,6 +39,8 @@ module system real(p) :: ccsd_e_tol = 1e-6 real(p) :: ccsd_t_tol = 1e-6 integer :: ccsd_diis_n_errmat = 8 + integer :: scf_maxiter = 50 + integer :: ccsd_maxiter = 50 ! Level of theory (up to) logical :: restricted @@ -63,13 +65,14 @@ subroutine read_system_in(sys) use error_handling, only: error type(system_t), intent(inout) :: sys real(p) :: scf_e_tol, scf_d_tol, ccsd_e_tol, ccsd_t_tol - integer :: scf_diis_n_errmat, ccsd_diis_n_errmat + integer :: scf_diis_n_errmat, ccsd_diis_n_errmat, scf_maxiter, ccsd_maxiter character(40) :: calc_type integer :: ir, ierr ! Define namelist - namelist /elsinput/ calc_type, scf_e_tol, scf_d_tol, scf_diis_n_errmat, ccsd_e_tol, ccsd_t_tol, ccsd_diis_n_errmat + namelist /elsinput/ calc_type, scf_e_tol, scf_d_tol, scf_diis_n_errmat, ccsd_e_tol, ccsd_t_tol, ccsd_diis_n_errmat, & + scf_maxiter, ccsd_maxiter ! Check if file exists inquire(file='dat/els.in', iostat=ierr) @@ -85,6 +88,7 @@ subroutine read_system_in(sys) sys%scf_e_tol = scf_e_tol; sys%scf_d_tol = scf_d_tol; sys%scf_diis_n_errmat = scf_diis_n_errmat sys%ccsd_e_tol = ccsd_e_tol; sys%ccsd_t_tol = ccsd_t_tol; sys%ccsd_diis_n_errmat = ccsd_diis_n_errmat + sys%scf_maxiter = scf_maxiter; sys%ccsd_maxiter = ccsd_maxiter select case(trim(calc_type)) case("RHF") From 155f7f222f118fb65c1127207728887cead11211 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Sat, 29 Jan 2022 14:09:38 +0000 Subject: [PATCH 67/71] Add util to generate integrals without symmetry. --- utils/psi4_integrals_nosym.py | 64 +++++++++++++++++++++++++++++++++++ 1 file changed, 64 insertions(+) create mode 100644 utils/psi4_integrals_nosym.py diff --git a/utils/psi4_integrals_nosym.py b/utils/psi4_integrals_nosym.py new file mode 100644 index 0000000..40a62a0 --- /dev/null +++ b/utils/psi4_integrals_nosym.py @@ -0,0 +1,64 @@ +#!/usr/bin/env python +# coding: utf-8 + +import psi4 +import numpy as np + +def lowtri_array_2d(end): + """ + Returns the lower triangular coordinates + lowtri_array_2d(3) = [[1,1],[2,1],[2,2],[3,1],[3,2],[3,3]] + """ + idx = [] + for i in range(end+1): + for j in range(i): + idx.append([i, j+1]) + return np.array(idx) + +def lowtri_array_4d(eri,end): + """ + Returns the 4d 'lower triangular' coordinates + lowtri_array_4d(3) = [[1,1,1,1],[2,1,1,1],[2,2,1,1],[2,2,2,1],[3,2],[3,3]] + """ + idx = [] + for i in range(end): + for j in range(i+1): + for k in range(i+1): + if k 1e-12: + idx.append([i+1,j+1,k+1,l+1,eri[i,j,k,l]]) + return np.array(idx) + +bl = 1.1 # Angstroms +ang = 104 # Degrees +psi4.set_memory('2000 MB') +mol = psi4.geometry(f""" + O + H 1 {bl} + H 1 {bl} 2 {ang} + units = angstrom + """) +psi4.set_options({'basis':'sto-3g'}) +wfn = psi4.core.Wavefunction(mol, psi4.core.BasisSet.build(mol)) +mints = psi4.core.MintsHelper(wfn.basisset()) +S = mints.ao_overlap().nph +T = mints.ao_kinetic().nph +V = mints.ao_potential().nph +eri = mints.ao_eri().nph + +nbasis = S[0].shape[0] +tril_array = lowtri_array_2d(nbasis) +indices = ((tril_array.T-1)[0],(tril_array.T-1)[1]) +s_dat = np.hstack((tril_array,np.array([S[0][indices]]).T)) +t_dat = np.hstack((tril_array,np.array([T[0][indices]]).T)) +v_dat = np.hstack((tril_array,np.array([V[0][indices]]).T)) +eri_dat = lowtri_array_4d(eri[0],7) + +np.savetxt('s.dat', s_dat, ['%1d','%1d','%17.15f'], delimiter='\t') +np.savetxt('t.dat', t_dat, ['%1d','%1d','%17.15f'], delimiter='\t') +np.savetxt('v.dat', v_dat, ['%1d','%1d','%17.15f'], delimiter='\t') +np.savetxt('eri.dat', eri_dat, ['%1d','%1d','%1d','%1d','%17.15f'], delimiter='\t') \ No newline at end of file From 28615703ab7cabd730fa122e67aaa3f575256140 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 31 Jan 2022 11:09:25 +0000 Subject: [PATCH 68/71] Refactor vectorise CCSD(T), add -ffast-math flag --- CMakeLists.txt | 2 +- dat/els.in | 2 +- src/ccsd.f90 | 110 ++++++++++++++++++++++++++++------------------ src/integrals.f90 | 2 + 4 files changed, 72 insertions(+), 44 deletions(-) diff --git a/CMakeLists.txt b/CMakeLists.txt index 7b46971..fdb711c 100644 --- a/CMakeLists.txt +++ b/CMakeLists.txt @@ -7,7 +7,7 @@ project (els) enable_language (Fortran) if (CMAKE_Fortran_COMPILER_ID MATCHES "GNU") - set (dialect "-ffree-form -std=f2008 -fimplicit-none -fopenmp -O3") + set (dialect "-ffree-form -std=f2008 -fimplicit-none -fopenmp -O3 -ffast-math") set (extras "-fcheck=all -Wall -ggdb -O0") endif () if (CMAKE_Fortran_COMPILER_ID MATCHES "Intel") diff --git a/dat/els.in b/dat/els.in index a4656a4..7a33927 100644 --- a/dat/els.in +++ b/dat/els.in @@ -1,5 +1,5 @@ &elsinput -calc_type="CCSD_spinorb", +calc_type="CCSD(T)_spinorb", scf_e_tol=1e-6, scf_d_tol=1e-7, scf_diis_n_errmat=6, diff --git a/src/ccsd.f90 b/src/ccsd.f90 index 0043ba2..c2dc0ce 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -66,7 +66,7 @@ subroutine do_ccsd_spinorb(sys, int_store) use integrals, only: int_store_t, eri_ind use error_handling, only: error, check_allocate - use system, only: state_t + use system, only: state_t, CCSD_T_spinorb type(system_t), intent(inout) :: sys type(int_store_t), intent(inout) :: int_store @@ -213,7 +213,7 @@ subroutine do_ccsd_spinorb(sys, int_store) ! ################### ! Iterative CC solver ! ################### - associate(nbasis=>sys%nbasis, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) + associate(nbasis=>sys%nbasis, nvirt=>sys%nvirt, nocc=>sys%nocc, t_ia=>cc_amp%t_ia, t_ijab=>cc_amp%t_ijab) do iter = 1, sys%ccsd_maxiter if (diis%use_diis) then ! These are for computing the error matrices for DIIS procedure @@ -240,6 +240,17 @@ subroutine do_ccsd_spinorb(sys, int_store) sys%e_ccsd = st%energy call move_alloc(cc_amp%t_ia, sys%t1) call move_alloc(cc_amp%t_ijab, sys%t2) + if (sys%calc_type == CCSD_T_spinorb) then + call move_alloc(cc_int%vovv, int_store%vovv) + call move_alloc(cc_int%ovoo, int_store%ovoo) + allocate(int_store%vvoo(nvirt,nvirt,nocc,nocc)) + int_store%vvoo = reshape(cc_int%oovv,shape(int_store%vvoo),order=(/3,4,1,2/)) + deallocate(cc_int%oooo, cc_int%ooov, cc_int%oovo, cc_int%oovv, cc_int%ovvo, cc_int%ovvv, & + cc_int%vvvv) + else + deallocate(cc_int%oooo, cc_int%ooov, cc_int%ovoo, cc_int%oovo, cc_int%oovv, cc_int%ovvo, cc_int%ovvv, & + cc_int%vovv, cc_int%vvvv) + end if exit end if call update_diis_cc(diis, cc_amp) @@ -1009,7 +1020,7 @@ subroutine do_ccsd_t_spinorb(sys, int_store) type(int_store_t), intent(in) :: int_store integer :: i, j, k, a, b, c, f, m, ierr - real(p), allocatable :: tmp_t3d(:,:,:), tmp_t3c(:,:,:), tmp_t3c_d(:,:,:) + real(p), dimension(:,:,:), allocatable :: tmp_t3d, tmp_t3c, tmp_t3c_d, reshape_tmp1, reshape_tmp2, t2_reshape(:,:,:,:) real(p) :: e_T integer, parameter :: iunit = 6 @@ -1017,61 +1028,76 @@ subroutine do_ccsd_t_spinorb(sys, int_store) write(iunit, '(1X, A)') 'CCSD(T)' write(iunit, '(1X, 10("-"))') - associate(nbasis=>sys%nbasis, nocc=>sys%nocc, e=>sys%canon_levels_spinorb, t1=>sys%t1, t2=>sys%t2,& - asym=>int_store%asym_spinorb) + associate(nvirt=>sys%nvirt, nocc=>sys%nocc, e=>sys%canon_levels_spinorb, t1=>sys%t1, t2=>sys%t2,& + vvoo=>int_store%vvoo,vovv=>int_store%vovv,ovoo=>int_store%ovoo) + + ! For efficient cache access during tmp_t3c updates + allocate(t2_reshape(nvirt,nvirt,nocc,nocc), source=0.0_p, stat=ierr) + call check_allocate('t2_reshape', (nvirt*nocc)**2, ierr) + ! ijab -> baij + t2_reshape = reshape(t2, shape(t2_reshape), order=(/4,3,2,1/)) + e_T = 0.0_p + !$omp parallel default(none) & - !$omp private(i, j, k, a, b, c, f, m, tmp_t3d, tmp_t3c, tmp_t3c_d, ierr) & - !$omp shared(sys, int_store, e_T) + !$omp private(tmp_t3d, tmp_t3c, tmp_t3c_d, ierr, reshape_tmp1, reshape_tmp2) & + !$omp shared(sys, int_store, t2_reshape) reduction(+:e_T) ! Declare heap-allocated arrays inside parallel region - allocate(tmp_t3d(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) - call check_allocate('tmp_t3d', 8*(nbasis-nocc)**3, ierr) - allocate(tmp_t3c(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) - call check_allocate('tmp_t3c', 8*(nbasis-nocc)**3, ierr) - allocate(tmp_t3c_d(2*nocc+1:2*nbasis,2*nocc+1:2*nbasis,2*nocc+1:2*nbasis), source=0.0_p, stat=ierr) - call check_allocate('tmp_t3c_d', 8*(nbasis-nocc)**3, ierr) + allocate(tmp_t3d(nvirt,nvirt,nvirt), source=0.0_p, stat=ierr) + call check_allocate('tmp_t3d', nvirt**3, ierr) + allocate(tmp_t3c(nvirt,nvirt,nvirt), source=0.0_p, stat=ierr) + call check_allocate('tmp_t3c', nvirt**3, ierr) + allocate(tmp_t3c_d(nvirt,nvirt,nvirt), source=0.0_p, stat=ierr) + call check_allocate('tmp_t3c_d', nvirt**3, ierr) + allocate(reshape_tmp1(nvirt,nvirt,nvirt), source=0.0_p, stat=ierr) + call check_allocate('reshape_tmp1', nvirt**3, ierr) + allocate(reshape_tmp2(nvirt,nvirt,nvirt), source=0.0_p, stat=ierr) + call check_allocate('reshape_tmp2', nvirt**3, ierr) ! We use avoid the storage of full triples (six-dimensional array..) and instead use the strategy of ! batched triples storage, denoted W^{ijk}(abc) in (https://doi.org/10.1016/0009-2614(91)87003-T). ! We could of course only compute one element in a loop iteration but that will probably result in bad floating point ! performance, here for each thread/loop iteration we use the Fortran intrinsic sum, ! instead of all relying on OMP reduction, to hopefully give better floating point performance. - !$omp do schedule(static, 10) collapse(3) reduction(+:e_T) - do i = 1, 2*nocc - do j = 1, 2*nocc - do k = 1, 2*nocc - ! Compute T3 amplitudes - do a = 2*nocc+1, 2*nbasis - do b = 2*nocc+1, 2*nbasis - do c = 2*nocc+1, 2*nbasis + + ! P(i/jk)P(a/bc) = (1-jik-kji)(1-bac-cba) + !$omp do schedule(static, 10) collapse(3) + do i = 1, nocc + do j = 1, nocc + do k = 1, nocc + ! Compute T3 amplitudes + do a = 1, nvirt + do c = 1, nvirt + do b = 1, nvirt ! Disonnected T3: D_{ijk}^{abc}*t_{ijk}^{abc}(d) = P(i/jk)P(a/bc)t_i^a* ! Can be rewritten directly as no sums in the expression - tmp_t3d(a,b,c) = - t1(i,a)*asym(c,b,j,k) + t1(j,a)*asym(c,b,i,k) + t1(k,a)*asym(c,b,j,i) & - + t1(i,b)*asym(c,a,j,k) - t1(j,b)*asym(c,a,i,k) - t1(k,b)*asym(c,a,j,i) & - - t1(i,c)*asym(j,k,b,a) + t1(j,c)*asym(i,k,b,a) + t1(k,c)*asym(j,i,b,a) - tmp_t3d(a,b,c) = tmp_t3d(a,b,c)/(e(i)+e(j)+e(k)-e(a)-e(b)-e(c)) - - ! Connected T3: D_{ijk}^{abc}*t_{ijk}^{abc}(c) = P(i/jk)P(a/bc)[\sum_f t_jk^af - \sum_m t_im^bc ] - ! Has to be zeroed as all terms are sums - tmp_t3c(a,b,c) = 0.0_p - do f = 2*nocc+1, 2*nbasis - tmp_t3c(a,b,c) = tmp_t3c(a,b,c) & - + t2(k,j,f,a)*asym(f,i,b,c) - t2(k,i,f,a)*asym(f,j,b,c) - t2(i,j,f,a)*asym(f,k,b,c) & - - t2(k,j,f,b)*asym(f,i,a,c) + t2(k,i,f,b)*asym(f,j,a,c) + t2(i,j,f,b)*asym(f,k,a,c) & - - t2(k,j,f,c)*asym(f,i,b,a) + t2(k,i,f,c)*asym(f,j,b,a) + t2(i,j,f,c)*asym(f,k,b,a) - end do - do m = 1, 2*nocc - tmp_t3c(a,b,c) = tmp_t3c(a,b,c) & - - t2(m,i,c,b)*asym(m,a,j,k) + t2(m,j,c,b)*asym(m,a,i,k) + t2(m,k,c,b)*asym(m,a,j,i) & - + t2(m,i,c,a)*asym(m,b,j,k) - t2(m,j,c,a)*asym(m,b,i,k) - t2(m,k,c,a)*asym(m,b,j,i) & - + t2(m,i,a,b)*asym(m,c,j,k) - t2(m,j,a,b)*asym(m,c,i,k) - t2(m,k,a,b)*asym(m,c,j,i) - end do - tmp_t3c_d(a,b,c) = tmp_t3c(a,b,c)/(e(i)+e(j)+e(k)-e(a)-e(b)-e(c)) + tmp_t3d(a,b,c) = (t1(i,a)*vvoo(b,c,j,k) - t1(j,a)*vvoo(b,c,i,k) - t1(k,a)*vvoo(b,c,j,i)) & + /(e(i)+e(j)+e(k)-e(a+nocc)-e(b+nocc)-e(c+nocc)) + + ! Connected T3: D_{ijk}^{abc}*t_{ijk}^{abc}(c) = + ! P(i/jk)P(a/bc)[\sum_f t_jk^af - \sum_m t_im^bc ] + tmp_t3c(a,b,c) = sum(vovv(:,i,b,c)*t2_reshape(:,a,k,j)) - sum(vovv(:,j,b,c)*t2_reshape(:,a,k,i)) & + - sum(vovv(:,k,b,c)*t2_reshape(:,a,i,j)) & + - sum(t2(:,i,c,b)*ovoo(:,a,j,k)) + sum(t2(:,j,c,b)*ovoo(:,a,i,k)) + sum(t2(:,k,c,b)*ovoo(:,a,j,i)) + + tmp_t3c_d(a,b,c) = tmp_t3c(a,b,c)/(e(i)+e(j)+e(k)-e(a+nocc)-e(b+nocc)-e(c+nocc)) end do end do end do + ! Do reshapes + reshape_tmp1 = reshape(tmp_t3d, shape(reshape_tmp1), order=(/2,1,3/)) + reshape_tmp2 = reshape(tmp_t3d, shape(reshape_tmp1), order=(/3,2,1/)) + tmp_t3d = tmp_t3d - reshape_tmp1 - reshape_tmp2 + reshape_tmp1 = reshape(tmp_t3c, shape(reshape_tmp1), order=(/2,1,3/)) + reshape_tmp2 = reshape(tmp_t3c, shape(reshape_tmp1), order=(/3,2,1/)) + tmp_t3c = tmp_t3c - reshape_tmp1 - reshape_tmp2 + + reshape_tmp1 = reshape(tmp_t3c_d, shape(reshape_tmp1), order=(/2,1,3/)) + reshape_tmp2 = reshape(tmp_t3c_d, shape(reshape_tmp1), order=(/3,2,1/)) + tmp_t3c_d = tmp_t3c_d - reshape_tmp1 - reshape_tmp2 + ! Calculate contributions e_T = e_T + sum(tmp_t3c*(tmp_t3c_d+tmp_t3d))/36 end do diff --git a/src/integrals.f90 b/src/integrals.f90 index 86812c2..71a20ed 100644 --- a/src/integrals.f90 +++ b/src/integrals.f90 @@ -30,6 +30,8 @@ module integrals real(p), allocatable :: eri(:) real(p), allocatable :: eri_mo(:) real(p), allocatable :: asym_spinorb(:,:,:,:) + ! needed for CCSD -> CCSD(T), spinorbital formulation + real(p), dimension(:,:,:,:), allocatable :: vvoo, vovv, ovoo end type int_store_t contains From 3306cd0214246b45dc9a02b8d17811efade7fe43 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 7 Feb 2022 17:09:04 +0000 Subject: [PATCH 69/71] Update README.md --- README.md | 1 + 1 file changed, 1 insertion(+) diff --git a/README.md b/README.md index a0d08da..49893c4 100644 --- a/README.md +++ b/README.md @@ -16,6 +16,7 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [X] DIIS acceleration for CCSD iterations - [X] Loop optimisations - cache - [X] User input file: level of theory, tolerances +- [X] BLAS acceleration of tensor contractions - [ ] Loop optimisations - using permutational symmetry - [ ] Adapting Hartree-Fock with symmetry - [ ] Ditto for MP2 From 61cffa9170af5014bdee98e1226af1c8ec48a23e Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 7 Feb 2022 17:12:35 +0000 Subject: [PATCH 70/71] Update README.md --- README.md | 2 ++ 1 file changed, 2 insertions(+) diff --git a/README.md b/README.md index 49893c4..e50d27d 100644 --- a/README.md +++ b/README.md @@ -17,6 +17,8 @@ The end goal of this project will be performing HF, MP2, CCSD, and CCSD(T), as p - [X] Loop optimisations - cache - [X] User input file: level of theory, tolerances - [X] BLAS acceleration of tensor contractions +- [ ] Spin-free CCSD +- [ ] Spin-free CCSD(T) - [ ] Loop optimisations - using permutational symmetry - [ ] Adapting Hartree-Fock with symmetry - [ ] Ditto for MP2 From 41cad727a3025aae4089a13b7067eebab5347598 Mon Sep 17 00:00:00 2001 From: Brian Zhao Date: Mon, 7 Feb 2022 22:24:47 +0000 Subject: [PATCH 71/71] Update dgemm interface --- src/ccsd.f90 | 15 ++++++--------- src/linalg.f90 | 14 +++++++++++--- 2 files changed, 17 insertions(+), 12 deletions(-) diff --git a/src/ccsd.f90 b/src/ccsd.f90 index c2dc0ce..2403caf 100644 --- a/src/ccsd.f90 +++ b/src/ccsd.f90 @@ -761,8 +761,7 @@ subroutine build_W(sys, cc_int, cc_amp) ! 1/2 tau_ijef allocate(reshape_scratch(nvirt,nvirt,nocc,nocc)) reshape_scratch = reshape(tau, shape(reshape_scratch), order=(/3,4,1,2/)) - call dgemm_wrapper('N','N',nocc**2,nocc**2,nvirt**2,cc_int%oovv,reshape_scratch,scratch) - W_oooo = W_oooo + scratch/2 + call dgemm_wrapper('N','N',nocc**2,nocc**2,nvirt**2,cc_int%oovv,reshape_scratch,W_oooo,0.5_dp,1.0_dp) deallocate(reshape_scratch) ! We reshape it to W_ijmn to make contractions more amenable to dgemm @@ -790,11 +789,11 @@ subroutine build_W(sys, cc_int, cc_amp) ! Eq. (8): W_mbej = + t_jf - t_nb - (1/2 t_jnfb + t_jf t_nb) ! ######################################################################################################################### ! + t_jf - allocate(scratch, reshape_scratch, mold=W_ovvo) - call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvv,t1,scratch) - W_ovvo = cc_int%ovvo + scratch + call dgemm_wrapper('N','T',nocc*nvirt**2,nocc,nvirt,cc_int%ovvv,t1,W_ovvo) + W_ovvo = W_ovvo + cc_int%ovvo ! - t_nb = +(t_bn)^T + allocate(scratch, reshape_scratch, mold=W_ovvo) call dgemm_wrapper('T','N',nvirt,nocc**2*nvirt,nocc,t1,cc_int%oovo,scratch) ! We need to reshape it because currently the scratch tensor is b,m,e,j reshape_scratch = reshape(scratch,shape(reshape_scratch),order=(/2,1,3,4/)) @@ -939,11 +938,9 @@ subroutine update_amplitudes(sys, cc_amp, int_store, cc_int) reshape_tmp = reshape(tmp_t2_s,shape(reshape_tmp),order=(/2,1,3,4/)) tmp_t2 = tmp_t2 - tmp_t2_s + reshape_tmp ! + 1/2 tau_mnab W_mnij, but remember out W_mnij is reshaped as W_ijmn - call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2_s) - tmp_t2 = tmp_t2 + tmp_t2_s/2 + call dgemm_wrapper('N','N',nocc**2,nvirt**2,nocc**2,W_oooo,tau,tmp_t2, 0.5_dp, 1.0_dp) ! + 1/2 tau_ijef W_abef - call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2_s) - tmp_t2 = tmp_t2 + tmp_t2_s/2 + call dgemm_wrapper('N','N',nocc**2,nvirt**2,nvirt**2,tau,W_vvvv,tmp_t2, 0.5_dp, 1.0_dp) deallocate(tmp_t2_s, reshape_tmp) t1 = tmp_t1 diff --git a/src/linalg.f90 b/src/linalg.f90 index 15e0f9f..c4aaa26 100644 --- a/src/linalg.f90 +++ b/src/linalg.f90 @@ -55,14 +55,16 @@ subroutine linsolve(A, B, ierr) end subroutine linsolve - subroutine dgemm_wrapper(transA, transB, outer_row, outer_col, inner_dim, A, B, C) + subroutine dgemm_wrapper(transA, transB, outer_row, outer_col, inner_dim, A, B, C, alpha, beta) ! Wraps around dgemm with fewer arguments character(1), intent(in) :: transA, transB integer, intent(in) :: outer_row, outer_col, inner_dim real(p), intent(in) :: A(*), B(*) + real(p), optional, intent(in) :: alpha, beta real(p), intent(inout) :: C(*) integer :: LDA, LDB + real(p) :: alpha_loc, beta_loc if (transA == 'T') then LDA = inner_dim @@ -75,9 +77,15 @@ subroutine dgemm_wrapper(transA, transB, outer_row, outer_col, inner_dim, A, B, else LDB = inner_dim end if + + alpha_loc = 1.0_p + if (present(alpha)) alpha_loc = alpha + + beta_loc = 0.0_p + if (present(beta)) beta_loc = beta - call dgemm(transA, transB, outer_row, outer_col, inner_dim, 1.0_dp, & - A, LDA, B, LDB, 0.0_dp, C, outer_row) + call dgemm(transA, transB, outer_row, outer_col, inner_dim, alpha_loc, & + A, LDA, B, LDB, beta_loc, C, outer_row) end subroutine dgemm_wrapper elemental subroutine zero_mat(matel)

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z`b31|Y8tsw8_~e;a;8t|DR`(a+VhrlWi8KanDyPiHrLWc~%FY^j{Og1IpCa_&y6!B!~W$?9`mqP?&@vKCP*hy`9Wca zU$S%KN3ePJ%jefRGztRO3;i!2WoE7X`1FN4MfT4|KmR*?-|SVqj8Rm}EsE+nGfWQq zF5KEuW5$1t5<@WxA5I1wJAr&A{vCKToaYxEQ1M3i>b}9btRrdD6CoX5eyVMd4W{&} ze*!X$Hy>W{k}|xZ)@$nA{b&i*b^`B4Pz4`+BUpt_eeYqmz*Y7dZEZ2jj7eQ?gBgR%PDI_&vyF+o~x5EXF%U$s4) zF@;{T%7}J}o7>nv;n2BHYEq&-EwkIM=!3db)abWfIinLl1?WJYcnK?W6{&G3fvHJIA%D)U!8R?nnmV=z`{T~I>3%LLQ diff --git a/Project#12/hints/hint1.md b/Project#12/hints/hint1.md deleted file mode 100644 index a05b2d7..0000000 --- a/Project#12/hints/hint1.md +++ /dev/null @@ -1,174 +0,0 @@ -Here is the CIS matrix for the same H2O STO-3G test case we've been using throughout these projects. Note that the row/column ordering follows *i* and *a* combinations with *a* as the faster-running index (i.e., *a* indexes the inner loop). Thus the first row/column corresponds to *i=0* and *a=0* and the second row/column to *i=0* and *a=1*. Notice that the matrix is diagonally dominant --- that is, the largest element on any row/column combination is the diagonal entry --- and that all the diagonal elements are positive. -``` - 1 2 3 4 5 6 7 8 9 10 - - 1 19.9847006 0.0000000 0.0000000 0.0000000 0.0000000 0.0261967 0.0000000 -0.0000000 0.0172405 0.0000000 - 2 0.0000000 19.9585039 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0074145 - 3 0.0000000 0.0000000 20.0308559 0.0000000 0.0000000 -0.0000000 0.0000000 0.0195218 0.0000000 0.0000000 - 4 0.0000000 0.0000000 0.0000000 20.0113341 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 5 0.0000000 0.0000000 0.0000000 0.0000000 19.9585039 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 6 0.0261967 0.0000000 -0.0000000 0.0000000 0.0000000 19.9847006 0.0000000 0.0000000 0.0098259 0.0000000 - 7 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 20.0113341 0.0000000 0.0000000 0.0000000 - 8 -0.0000000 0.0000000 0.0195218 0.0000000 0.0000000 0.0000000 0.0000000 20.0308559 0.0000000 0.0000000 - 9 0.0172405 0.0000000 0.0000000 0.0000000 0.0000000 0.0098259 0.0000000 0.0000000 1.1883321 0.0000000 - 10 0.0000000 0.0074145 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 1.0931793 - 11 0.0000000 0.0000000 0.0280239 0.0000000 0.0000000 0.0000000 0.0000000 0.0191033 0.0000000 0.0000000 - 12 0.0000000 -0.0000000 0.0000000 0.0089205 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 13 0.0000000 0.0000000 0.0000000 0.0000000 0.0074145 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 14 0.0098259 0.0000000 0.0000000 0.0000000 0.0000000 0.0172405 0.0000000 0.0000000 0.0951527 0.0000000 - 15 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0089205 0.0000000 0.0000000 0.0000000 - 16 0.0000000 0.0000000 0.0191033 0.0000000 0.0000000 0.0000000 0.0000000 0.0280239 -0.0000000 0.0000000 - 17 -0.0000000 0.0000000 -0.0046225 0.0000000 0.0000000 -0.0000000 0.0000000 0.0030386 0.0000000 0.0000000 - 18 0.0000000 -0.0000000 0.0000000 -0.0076611 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 19 -0.0134310 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0057699 0.0000000 0.0000000 -0.0178319 0.0000000 - 20 0.0000000 -0.0076611 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0867137 - 21 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0076611 0.0000000 0.0000000 0.0000000 - 22 -0.0000000 0.0000000 0.0030386 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0046225 0.0000000 0.0000000 - 23 0.0000000 0.0000000 0.0000000 0.0000000 -0.0076611 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 24 -0.0057699 0.0000000 0.0000000 0.0000000 0.0000000 -0.0134310 0.0000000 -0.0000000 0.0688817 0.0000000 - 25 0.0197793 0.0000000 -0.0000000 0.0000000 0.0000000 0.0017709 0.0000000 0.0000000 -0.0117148 0.0000000 - 26 0.0000000 0.0180084 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0485372 - 27 0.0000000 0.0000000 0.0149879 0.0000000 0.0000000 0.0000000 0.0000000 0.0112477 0.0000000 0.0000000 - 28 0.0000000 -0.0000000 0.0000000 0.0037402 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 29 0.0000000 0.0000000 0.0000000 0.0000000 0.0180084 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 30 0.0017709 0.0000000 0.0000000 0.0000000 0.0000000 0.0197793 0.0000000 -0.0000000 -0.0602520 0.0000000 - 31 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0037402 0.0000000 0.0000000 0.0000000 - 32 0.0000000 0.0000000 0.0112477 0.0000000 0.0000000 0.0000000 0.0000000 0.0149879 0.0000000 0.0000000 - 33 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 34 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 35 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 36 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 37 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 38 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 39 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 40 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 - - 11 12 13 14 15 16 17 18 19 20 - - 1 0.0000000 0.0000000 0.0000000 0.0098259 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0134310 0.0000000 - 2 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0076611 - 3 0.0280239 0.0000000 0.0000000 0.0000000 0.0000000 0.0191033 -0.0046225 0.0000000 -0.0000000 0.0000000 - 4 0.0000000 0.0089205 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0076611 0.0000000 -0.0000000 - 5 0.0000000 0.0000000 0.0074145 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 6 0.0000000 0.0000000 0.0000000 0.0172405 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0057699 0.0000000 - 7 0.0000000 0.0000000 -0.0000000 0.0000000 0.0089205 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 8 0.0191033 0.0000000 0.0000000 0.0000000 0.0000000 0.0280239 0.0030386 0.0000000 0.0000000 0.0000000 - 9 0.0000000 0.0000000 0.0000000 0.0951527 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0178319 0.0000000 - 10 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0867137 - 11 1.2566569 0.0000000 0.0000000 -0.0000000 0.0000000 0.0678165 -0.0564572 0.0000000 0.0000000 0.0000000 - 12 0.0000000 1.1888405 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0867137 0.0000000 0.0000000 - 13 0.0000000 0.0000000 1.0931793 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 14 -0.0000000 0.0000000 0.0000000 1.1883321 0.0000000 0.0000000 0.0000000 0.0000000 0.0688817 0.0000000 - 15 0.0000000 0.0000000 0.0000000 0.0000000 1.1888405 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 16 0.0678165 0.0000000 0.0000000 0.0000000 0.0000000 1.2566569 0.0302565 0.0000000 -0.0000000 0.0000000 - 17 -0.0564572 0.0000000 0.0000000 0.0000000 0.0000000 0.0302565 0.5507646 0.0000000 0.0000000 0.0000000 - 18 0.0000000 -0.0867137 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.4757743 0.0000000 0.0000000 - 19 0.0000000 0.0000000 0.0000000 0.0688817 0.0000000 -0.0000000 0.0000000 0.0000000 0.7122157 0.0000000 - 20 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.5527668 - 21 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0867137 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 22 0.0302565 0.0000000 0.0000000 0.0000000 0.0000000 -0.0564572 0.0749902 0.0000000 0.0000000 0.0000000 - 23 0.0000000 0.0000000 -0.0867137 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 24 -0.0000000 0.0000000 0.0000000 -0.0178319 0.0000000 0.0000000 0.0000000 0.0000000 0.1594489 0.0000000 - 25 0.0000000 0.0000000 0.0000000 -0.0602520 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0383679 0.0000000 - 26 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0615255 - 27 -0.0011401 0.0000000 0.0000000 0.0000000 0.0000000 0.0171886 0.0073884 0.0000000 -0.0000000 0.0000000 - 28 0.0000000 -0.0183287 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0615255 0.0000000 -0.0000000 - 29 0.0000000 0.0000000 0.0485372 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 30 0.0000000 0.0000000 0.0000000 -0.0117148 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0998933 0.0000000 - 31 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0183287 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 32 0.0171886 0.0000000 0.0000000 0.0000000 0.0000000 -0.0011401 -0.0541371 0.0000000 0.0000000 0.0000000 - 33 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 - 34 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 35 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 36 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 37 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 38 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 - 39 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 40 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 - - 21 22 23 24 25 26 27 28 29 30 - - 1 0.0000000 -0.0000000 0.0000000 -0.0057699 0.0197793 0.0000000 0.0000000 0.0000000 0.0000000 0.0017709 - 2 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0180084 0.0000000 -0.0000000 0.0000000 0.0000000 - 3 0.0000000 0.0030386 0.0000000 0.0000000 -0.0000000 0.0000000 0.0149879 0.0000000 0.0000000 0.0000000 - 4 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0037402 0.0000000 0.0000000 - 5 -0.0000000 0.0000000 -0.0076611 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0180084 0.0000000 - 6 0.0000000 -0.0000000 0.0000000 -0.0134310 0.0017709 0.0000000 0.0000000 0.0000000 0.0000000 0.0197793 - 7 -0.0076611 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 8 0.0000000 -0.0046225 0.0000000 -0.0000000 0.0000000 0.0000000 0.0112477 0.0000000 0.0000000 -0.0000000 - 9 0.0000000 0.0000000 0.0000000 0.0688817 -0.0117148 0.0000000 0.0000000 0.0000000 0.0000000 -0.0602520 - 10 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0485372 0.0000000 -0.0000000 0.0000000 0.0000000 - 11 0.0000000 0.0302565 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0011401 0.0000000 0.0000000 0.0000000 - 12 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0183287 0.0000000 0.0000000 - 13 -0.0000000 0.0000000 -0.0867137 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0485372 0.0000000 - 14 0.0000000 0.0000000 0.0000000 -0.0178319 -0.0602520 0.0000000 0.0000000 0.0000000 0.0000000 -0.0117148 - 15 -0.0867137 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 16 0.0000000 -0.0564572 0.0000000 0.0000000 0.0000000 0.0000000 0.0171886 0.0000000 0.0000000 0.0000000 - 17 0.0000000 0.0749902 0.0000000 0.0000000 -0.0000000 0.0000000 0.0073884 0.0000000 0.0000000 -0.0000000 - 18 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0615255 0.0000000 0.0000000 - 19 0.0000000 0.0000000 0.0000000 0.1594489 -0.0383679 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0998933 - 20 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0615255 0.0000000 -0.0000000 0.0000000 0.0000000 - 21 0.4757743 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 22 0.0000000 0.5507646 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0541371 0.0000000 0.0000000 -0.0000000 - 23 0.0000000 0.0000000 0.5527668 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0615255 0.0000000 - 24 0.0000000 0.0000000 0.0000000 0.7122157 -0.0998933 0.0000000 0.0000000 0.0000000 0.0000000 -0.0383679 - 25 0.0000000 -0.0000000 0.0000000 -0.0998933 0.4658980 0.0000000 0.0000000 0.0000000 0.0000000 0.0955699 - 26 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.3703281 0.0000000 -0.0000000 0.0000000 0.0000000 - 27 0.0000000 -0.0541371 0.0000000 0.0000000 0.0000000 0.0000000 0.5152458 0.0000000 0.0000000 0.0000000 - 28 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.4442931 0.0000000 0.0000000 - 29 0.0000000 0.0000000 0.0615255 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.3703281 0.0000000 - 30 0.0000000 -0.0000000 0.0000000 -0.0383679 0.0955699 0.0000000 0.0000000 0.0000000 0.0000000 0.4658980 - 31 0.0615255 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 32 0.0000000 0.0073884 0.0000000 -0.0000000 0.0000000 0.0000000 0.0709527 0.0000000 0.0000000 0.0000000 - 33 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 34 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 35 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 36 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 37 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 38 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 39 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 40 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - - 31 32 33 34 35 36 37 38 39 40 - - 1 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 2 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 3 0.0000000 0.0112477 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 4 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 5 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 6 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 7 0.0037402 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 8 0.0000000 0.0149879 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 9 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 - 10 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 11 0.0000000 0.0171886 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 12 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 13 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 14 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 15 -0.0183287 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 16 0.0000000 -0.0011401 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 17 0.0000000 -0.0541371 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 - 18 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 19 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 - 20 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 21 0.0615255 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 22 0.0000000 0.0073884 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 23 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 24 0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 - 25 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 26 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 27 0.0000000 0.0709527 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 28 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 29 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 30 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 31 0.4442931 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 32 0.0000000 0.5152458 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 33 0.0000000 0.0000000 0.3218586 0.0000000 0.0000000 0.0000000 0.0000000 0.0346031 0.0000000 -0.0000000 - 34 0.0000000 0.0000000 0.0000000 0.2872555 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 35 0.0000000 0.0000000 0.0000000 0.0000000 0.3910304 0.0000000 0.0000000 -0.0000000 0.0000000 0.0250414 - 36 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.3659890 0.0000000 0.0000000 0.0000000 0.0000000 - 37 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.2872555 0.0000000 0.0000000 0.0000000 - 38 0.0000000 -0.0000000 0.0346031 0.0000000 -0.0000000 0.0000000 0.0000000 0.3218586 0.0000000 0.0000000 - 39 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.3659890 0.0000000 - 40 0.0000000 0.0000000 -0.0000000 0.0000000 0.0250414 0.0000000 0.0000000 0.0000000 0.0000000 0.3910304 -``` diff --git a/Project#12/hints/hint2.md b/Project#12/hints/hint2.md deleted file mode 100644 index 10c5901..0000000 --- a/Project#12/hints/hint2.md +++ /dev/null @@ -1,16 +0,0 @@ -Here is the CIS spin-adapted singlet matrix for the H2O STO-3G test case. Note that the row/column ordering follows *i* and *a* combinations with *a* as the faster-running index (i.e., *a* indexes the inner loop). Thus the first row/column corresponds to *i=0* and *a=0* and the second row/column to *i=0* and *a=1*. Notice that the matrix is diagonally dominant --- that is, the largest element on any row/column combination is the diagonal entry --- and that all the diagonal elements are positive. -``` - 1 2 3 4 5 6 7 8 9 10 - - 1 20.0108972 0.0000000 0.0270664 0.0000000 -0.0000000 -0.0192010 0.0215503 0.0000000 -0.0000000 0.0000000 - 2 0.0000000 20.0503777 0.0000000 0.0471272 -0.0015840 -0.0000000 -0.0000000 0.0262356 0.0000000 -0.0000000 - 3 0.0270664 0.0000000 1.2834848 -0.0000000 0.0000000 0.0510498 -0.0719668 0.0000000 -0.0000000 -0.0000000 - 4 0.0000000 0.0471272 -0.0000000 1.3244734 -0.0262007 0.0000000 0.0000000 0.0160485 0.0000000 0.0000000 - 5 -0.0000000 -0.0015840 0.0000000 -0.0262007 0.6257548 0.0000000 -0.0000000 -0.0467487 -0.0000000 -0.0000000 - 6 -0.0192010 -0.0000000 0.0510498 0.0000000 0.0000000 0.8716646 -0.1382612 -0.0000000 -0.0000000 -0.0000000 - 7 0.0215503 -0.0000000 -0.0719668 0.0000000 -0.0000000 -0.1382612 0.5614679 0.0000000 0.0000000 0.0000000 - 8 0.0000000 0.0262356 0.0000000 0.0160485 -0.0467487 -0.0000000 0.0000000 0.5861985 0.0000000 0.0000000 - 9 -0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 0.3564618 0.0000000 - 10 0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.4160717 - -``` diff --git a/Project#12/hints/hint3.md b/Project#12/hints/hint3.md deleted file mode 100644 index 13b0e43..0000000 --- a/Project#12/hints/hint3.md +++ /dev/null @@ -1,666 +0,0 @@ -Here is the TDHF/RPA version of the H2O STO-3G Hamitlonian. The row/column ordering is the same as for CIS above, but there two blocks of *i/a* pairs, one for each of the ***A*** and ***B*** submatrices. This matrix is also diagonally dominant, but not all the diagonal elements are positive. -``` - 1 2 3 4 5 6 7 8 9 10 - - 1 19.9847006 0.0000000 0.0000000 0.0000000 0.0000000 0.0261967 0.0000000 -0.0000000 0.0172405 0.0000000 - 2 0.0000000 19.9585039 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0074145 - 3 0.0000000 0.0000000 20.0308559 0.0000000 0.0000000 -0.0000000 0.0000000 0.0195218 0.0000000 0.0000000 - 4 0.0000000 0.0000000 0.0000000 20.0113341 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 5 0.0000000 0.0000000 0.0000000 0.0000000 19.9585039 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 6 0.0261967 0.0000000 -0.0000000 0.0000000 0.0000000 19.9847006 0.0000000 0.0000000 0.0098259 0.0000000 - 7 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 20.0113341 0.0000000 0.0000000 0.0000000 - 8 -0.0000000 0.0000000 0.0195218 0.0000000 0.0000000 0.0000000 0.0000000 20.0308559 0.0000000 0.0000000 - 9 0.0172405 0.0000000 0.0000000 0.0000000 0.0000000 0.0098259 0.0000000 0.0000000 1.1883321 0.0000000 - 10 0.0000000 0.0074145 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 1.0931793 - 11 0.0000000 0.0000000 0.0280239 0.0000000 0.0000000 0.0000000 0.0000000 0.0191033 0.0000000 0.0000000 - 12 0.0000000 -0.0000000 0.0000000 0.0089205 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 13 0.0000000 0.0000000 0.0000000 0.0000000 0.0074145 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 14 0.0098259 0.0000000 0.0000000 0.0000000 0.0000000 0.0172405 0.0000000 0.0000000 0.0951527 0.0000000 - 15 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0089205 0.0000000 0.0000000 0.0000000 - 16 0.0000000 0.0000000 0.0191033 0.0000000 0.0000000 0.0000000 0.0000000 0.0280239 -0.0000000 0.0000000 - 17 -0.0000000 0.0000000 -0.0046225 0.0000000 0.0000000 -0.0000000 0.0000000 0.0030386 0.0000000 0.0000000 - 18 0.0000000 -0.0000000 0.0000000 -0.0076611 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 19 -0.0134310 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0057699 0.0000000 0.0000000 -0.0178319 0.0000000 - 20 0.0000000 -0.0076611 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0867137 - 21 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0076611 0.0000000 0.0000000 0.0000000 - 22 -0.0000000 0.0000000 0.0030386 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0046225 0.0000000 0.0000000 - 23 0.0000000 0.0000000 0.0000000 0.0000000 -0.0076611 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 24 -0.0057699 0.0000000 0.0000000 0.0000000 0.0000000 -0.0134310 0.0000000 -0.0000000 0.0688817 0.0000000 - 25 0.0197793 0.0000000 -0.0000000 0.0000000 0.0000000 0.0017709 0.0000000 0.0000000 -0.0117148 0.0000000 - 26 0.0000000 0.0180084 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0485372 - 27 0.0000000 0.0000000 0.0149879 0.0000000 0.0000000 0.0000000 0.0000000 0.0112477 0.0000000 0.0000000 - 28 0.0000000 -0.0000000 0.0000000 0.0037402 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 29 0.0000000 0.0000000 0.0000000 0.0000000 0.0180084 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 30 0.0017709 0.0000000 0.0000000 0.0000000 0.0000000 0.0197793 0.0000000 -0.0000000 -0.0602520 0.0000000 - 31 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0037402 0.0000000 0.0000000 0.0000000 - 32 0.0000000 0.0000000 0.0112477 0.0000000 0.0000000 0.0000000 0.0000000 0.0149879 0.0000000 0.0000000 - 33 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 34 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 35 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 36 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 37 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 38 -0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 39 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 - 40 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 - 41 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0261967 -0.0000000 0.0000000 -0.0000000 -0.0000000 - 42 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0261967 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 43 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0195218 -0.0000000 -0.0000000 - 44 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0195218 -0.0000000 -0.0000000 -0.0000000 - 45 -0.0000000 0.0261967 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0098259 - 46 -0.0261967 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0098259 -0.0000000 - 47 -0.0000000 -0.0000000 -0.0000000 0.0195218 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 - 48 0.0000000 -0.0000000 -0.0195218 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 49 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0098259 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 50 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0098259 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 - 51 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0191033 -0.0000000 -0.0000000 - 52 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0191033 -0.0000000 -0.0000000 -0.0000000 - 53 -0.0000000 0.0098259 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0951527 - 54 -0.0098259 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0951527 -0.0000000 - 55 -0.0000000 0.0000000 -0.0000000 0.0191033 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 56 -0.0000000 -0.0000000 -0.0191033 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 - 57 -0.0000000 -0.0000000 -0.0088085 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0030386 -0.0000000 -0.0000000 - 58 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0057699 -0.0000000 -0.0000000 -0.0000000 - 59 0.0088085 0.0000000 -0.0000000 -0.0000000 0.0000000 0.0057699 -0.0000000 -0.0000000 -0.0386252 -0.0000000 - 60 0.0000000 0.0000000 -0.0000000 -0.0000000 0.0030386 0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 - 61 -0.0000000 -0.0000000 -0.0000000 -0.0057699 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 - 62 0.0000000 -0.0000000 -0.0030386 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0088085 -0.0000000 -0.0000000 - 63 0.0000000 0.0030386 -0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0302565 - 64 0.0057699 0.0000000 -0.0000000 -0.0000000 0.0000000 0.0088085 -0.0000000 -0.0000000 -0.0688817 -0.0000000 - 65 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0017709 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 66 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0017709 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 - 67 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0112477 0.0000000 -0.0000000 - 68 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0112477 -0.0000000 -0.0000000 -0.0000000 - 69 -0.0000000 0.0017709 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0602520 - 70 -0.0017709 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0602520 -0.0000000 - 71 -0.0000000 0.0000000 -0.0000000 0.0112477 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 - 72 -0.0000000 -0.0000000 -0.0112477 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 73 -0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 - 74 -0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 - 75 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 - 76 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 - 77 -0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 - 78 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 79 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 80 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 - - 11 12 13 14 15 16 17 18 19 20 - - 1 0.0000000 0.0000000 0.0000000 0.0098259 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0134310 0.0000000 - 2 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0076611 - 3 0.0280239 0.0000000 0.0000000 0.0000000 0.0000000 0.0191033 -0.0046225 0.0000000 -0.0000000 0.0000000 - 4 0.0000000 0.0089205 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0076611 0.0000000 -0.0000000 - 5 0.0000000 0.0000000 0.0074145 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 6 0.0000000 0.0000000 0.0000000 0.0172405 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0057699 0.0000000 - 7 0.0000000 0.0000000 -0.0000000 0.0000000 0.0089205 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 8 0.0191033 0.0000000 0.0000000 0.0000000 0.0000000 0.0280239 0.0030386 0.0000000 0.0000000 0.0000000 - 9 0.0000000 0.0000000 0.0000000 0.0951527 0.0000000 -0.0000000 0.0000000 0.0000000 -0.0178319 0.0000000 - 10 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0867137 - 11 1.2566569 0.0000000 0.0000000 -0.0000000 0.0000000 0.0678165 -0.0564572 0.0000000 0.0000000 0.0000000 - 12 0.0000000 1.1888405 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0867137 0.0000000 0.0000000 - 13 0.0000000 0.0000000 1.0931793 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 14 -0.0000000 0.0000000 0.0000000 1.1883321 0.0000000 0.0000000 0.0000000 0.0000000 0.0688817 0.0000000 - 15 0.0000000 0.0000000 0.0000000 0.0000000 1.1888405 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 16 0.0678165 0.0000000 0.0000000 0.0000000 0.0000000 1.2566569 0.0302565 0.0000000 -0.0000000 0.0000000 - 17 -0.0564572 0.0000000 0.0000000 0.0000000 0.0000000 0.0302565 0.5507646 0.0000000 0.0000000 0.0000000 - 18 0.0000000 -0.0867137 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.4757743 0.0000000 0.0000000 - 19 0.0000000 0.0000000 0.0000000 0.0688817 0.0000000 -0.0000000 0.0000000 0.0000000 0.7122157 0.0000000 - 20 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.5527668 - 21 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0867137 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 22 0.0302565 0.0000000 0.0000000 0.0000000 0.0000000 -0.0564572 0.0749902 0.0000000 0.0000000 0.0000000 - 23 0.0000000 0.0000000 -0.0867137 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 24 -0.0000000 0.0000000 0.0000000 -0.0178319 0.0000000 0.0000000 0.0000000 0.0000000 0.1594489 0.0000000 - 25 0.0000000 0.0000000 0.0000000 -0.0602520 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0383679 0.0000000 - 26 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0615255 - 27 -0.0011401 0.0000000 0.0000000 0.0000000 0.0000000 0.0171886 0.0073884 0.0000000 -0.0000000 0.0000000 - 28 0.0000000 -0.0183287 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0615255 0.0000000 -0.0000000 - 29 0.0000000 0.0000000 0.0485372 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 30 0.0000000 0.0000000 0.0000000 -0.0117148 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0998933 0.0000000 - 31 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0183287 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 32 0.0171886 0.0000000 0.0000000 0.0000000 0.0000000 -0.0011401 -0.0541371 0.0000000 0.0000000 0.0000000 - 33 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 - 34 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 - 35 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 - 36 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 - 37 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 38 -0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 - 39 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 - 40 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 - 41 0.0000000 -0.0000000 -0.0000000 -0.0098259 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0088085 0.0000000 - 42 -0.0000000 -0.0000000 0.0098259 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 - 43 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0191033 -0.0088085 -0.0000000 -0.0000000 -0.0000000 - 44 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0191033 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 45 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0030386 - 46 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 0.0000000 -0.0000000 0.0057699 0.0000000 - 47 -0.0000000 0.0191033 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0057699 -0.0000000 0.0000000 - 48 -0.0191033 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0030386 -0.0000000 -0.0000000 -0.0000000 - 49 -0.0000000 -0.0000000 -0.0000000 -0.0951527 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0386252 -0.0000000 - 50 -0.0000000 -0.0000000 0.0951527 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 51 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0678165 0.0386252 -0.0000000 -0.0000000 -0.0000000 - 52 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0678165 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 53 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0302565 - 54 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0688817 -0.0000000 - 55 -0.0000000 0.0678165 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0688817 -0.0000000 -0.0000000 - 56 -0.0678165 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0302565 -0.0000000 0.0000000 -0.0000000 - 57 0.0386252 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0302565 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 58 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0688817 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 59 -0.0000000 -0.0000000 -0.0000000 -0.0688817 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 60 -0.0000000 -0.0000000 0.0302565 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 61 -0.0000000 0.0688817 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0749902 -0.0000000 0.0000000 - 62 -0.0302565 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0386252 -0.0749902 -0.0000000 -0.0000000 -0.0000000 - 63 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.1594489 - 64 0.0000000 -0.0000000 -0.0000000 -0.0386252 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.1594489 -0.0000000 - 65 -0.0000000 -0.0000000 -0.0000000 0.0602520 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0457562 -0.0000000 - 66 -0.0000000 -0.0000000 -0.0602520 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 67 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0171886 -0.0457562 -0.0000000 -0.0000000 -0.0000000 - 68 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0171886 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 69 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0541371 - 70 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0998933 -0.0000000 - 71 -0.0000000 0.0171886 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0998933 -0.0000000 0.0000000 - 72 -0.0171886 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0541371 -0.0000000 -0.0000000 -0.0000000 - 73 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 - 74 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 75 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 76 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 77 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 78 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 - 79 -0.0000000 0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 -0.0000000 - 80 -0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 -0.0000000 0.0000000 -0.0000000 0.0000000 -0.0000000 - - 21 22 23 24 25 26 27 28 29 30 - - 1 0.0000000 -0.0000000 0.0000000 -0.0057699 0.0197793 0.0000000 0.0000000 0.0000000 0.0000000 0.0017709 - 2 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0180084 0.0000000 -0.0000000 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file mode 100644 index feb8199..0000000 --- a/Project#12/input/ch4/STO-3G/enuc.dat +++ /dev/null @@ -1 +0,0 @@ - 13.497304462036480 diff --git a/Project#12/input/ch4/STO-3G/eri.dat b/Project#12/input/ch4/STO-3G/eri.dat deleted file mode 100644 index b1c1a16..0000000 --- a/Project#12/input/ch4/STO-3G/eri.dat +++ /dev/null @@ -1,912 +0,0 @@ - 1 1 1 1 3.541948297688456 - 2 1 1 1 0.576921328341946 - 2 2 1 1 0.854681772892244 - 2 1 2 1 0.111888125975301 - 2 2 2 1 0.205283870818581 - 2 2 2 2 0.624708798510611 - 3 3 1 1 0.852436095451127 - 4 4 1 1 0.852436095451127 - 5 5 1 1 0.852436095451127 - 3 1 3 1 0.020296465970775 - 4 1 4 1 0.020296465970775 - 5 1 5 1 0.020296465970775 - 3 3 2 1 0.205335088917950 - 4 4 2 1 0.205335088917950 - 5 5 2 1 0.205335088917950 - 3 2 3 1 0.030857749607787 - 4 2 4 1 0.030857749607787 - 5 2 5 1 0.030857749607787 - 3 3 2 2 0.624568373997849 - 4 4 2 2 0.624568373997849 - 5 5 2 2 0.624568373997849 - 3 2 3 2 0.137996275062609 - 4 2 4 2 0.137996275062609 - 5 2 5 2 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0.012847889010515 - 9 9 8 8 0.296353939081570 - 9 8 9 8 0.015770501299918 - 9 9 9 1 0.031703797879678 - 9 9 9 2 0.304981529941436 - 9 9 9 3 -0.206879432071914 - 9 9 9 4 -0.206879432071914 - 9 9 9 5 0.206879432071914 - 9 9 9 6 0.085276746780538 - 9 9 9 7 0.085276746780538 - 9 9 9 8 0.085276746780538 - 9 9 9 9 0.774605895725855 diff --git a/Project#12/input/ch4/STO-3G/geom.dat b/Project#12/input/ch4/STO-3G/geom.dat deleted file mode 100644 index 9c536a9..0000000 --- a/Project#12/input/ch4/STO-3G/geom.dat +++ /dev/null @@ -1,6 +0,0 @@ -5 -6.000000000000 -0.000000000000 0.000000000000 0.000000000000 -1.000000000000 1.183771681898 -1.183771681898 -1.183771681898 -1.000000000000 1.183771681898 1.183771681898 1.183771681898 -1.000000000000 -1.183771681898 1.183771681898 -1.183771681898 -1.000000000000 -1.183771681898 -1.183771681898 1.183771681898 diff --git a/Project#12/input/ch4/STO-3G/input.dat b/Project#12/input/ch4/STO-3G/input.dat deleted file mode 100644 index 6dfb483..0000000 --- a/Project#12/input/ch4/STO-3G/input.dat +++ /dev/null @@ -1,43 +0,0 @@ -psi: ( - label = "CH4 SCF Test Case" - wfn = scf - jobtype = oeprop - reference = rhf - basis = "STO-3G" - units = angstrom - subgroup = c1 - delete_tei = false - delete_oei = false - zmat = ( - C - H 1 r - H 1 r 2 td - H 1 r 2 td 3 d - H 1 r 2 td 4 d - ) - zvars = ( - r 1.085 - td 109.47122063449069136958 - d 120.0 - ) -) - -basis: ( - carbon: "STO-3G" = - ( (S ( 71.61683730 0.15432900) - ( 13.04509630 0.53532810) - ( 3.53051220 0.44463450) ) - (S ( 2.94124940 -0.09996720) - ( 0.68348310 0.39951280) - ( 0.22228990 0.70011550) ) - (P ( 2.94124940 0.15591630) - ( 0.68348310 0.60768370) - ( 0.22228990 0.39195740) ) - ) - - hydrogen: "STO-3G"= - ( (S ( 3.42525090 0.15432890) - ( 0.62391370 0.53532810) - ( 0.16885540 0.44463450) ) - ) -) diff --git a/Project#12/input/ch4/STO-3G/mux.dat b/Project#12/input/ch4/STO-3G/mux.dat deleted file mode 100644 index 9dca8dd..0000000 --- a/Project#12/input/ch4/STO-3G/mux.dat +++ /dev/null @@ -1,45 +0,0 @@ - 1 1 0.000000000000000 - 2 1 0.000000000000000 - 2 2 0.000000000000000 - 3 1 -0.071855488532817 - 3 2 -0.838743574800986 - 3 3 0.000000000000000 - 4 1 -0.000000000000000 - 4 2 0.000000000000000 - 4 3 -0.000000000000000 - 4 4 0.000000000000000 - 5 1 0.000000000000000 - 5 2 0.000000000000000 - 5 3 -0.000000000000000 - 5 4 0.000000000000000 - 5 5 0.000000000000000 - 6 1 -0.004780775261548 - 6 2 -0.306592476518555 - 6 3 -0.519567036508228 - 6 4 0.163831354490276 - 6 5 0.163831354490276 - 6 6 -1.183771681897730 - 7 1 -0.004780775261548 - 7 2 -0.306592476518555 - 7 3 -0.519567036508228 - 7 4 -0.163831354490276 - 7 5 -0.163831354490276 - 7 6 -0.202918556316052 - 7 7 -1.183771681897730 - 8 1 0.004780775261548 - 8 2 0.306592476518555 - 8 3 -0.519567036508228 - 8 4 0.163831354490276 - 8 5 -0.163831354490276 - 8 6 -0.000000000000000 - 8 7 -0.000000000000000 - 8 8 1.183771681897730 - 9 1 0.004780775261548 - 9 2 0.306592476518555 - 9 3 -0.519567036508228 - 9 4 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0.161483959338374 - 7 7 7 6 0.091353706761488 - 7 7 7 7 0.774605943919898 diff --git a/Project#12/input/h2o/STO-3G/geom.dat b/Project#12/input/h2o/STO-3G/geom.dat deleted file mode 100644 index 99b165d..0000000 --- a/Project#12/input/h2o/STO-3G/geom.dat +++ /dev/null @@ -1,4 +0,0 @@ -3 -8.000000000000 0.000000000000 -0.143225816552 0.000000000000 -1.000000000000 1.638036840407 1.136548822547 -0.000000000000 -1.000000000000 -1.638036840407 1.136548822547 -0.000000000000 diff --git a/Project#12/input/h2o/STO-3G/input.dat b/Project#12/input/h2o/STO-3G/input.dat deleted file mode 100644 index f8c5067..0000000 --- a/Project#12/input/h2o/STO-3G/input.dat +++ /dev/null @@ -1,12 +0,0 @@ -psi: ( - label = "H2O SCF Test Case" - memory = (10.0 MB) - wfn = scf - jobtype = oeprop - delete_tei = false - delete_oei = false - reference = rhf - basis = "STO-3G" - subgroup = c1 - zmat = ((o) (h 1 1.1) (h 1 1.1 2 104.0)) -) diff --git a/Project#12/input/h2o/STO-3G/mux.dat b/Project#12/input/h2o/STO-3G/mux.dat deleted file mode 100644 index c5d92c5..0000000 --- a/Project#12/input/h2o/STO-3G/mux.dat +++ /dev/null @@ -1,28 +0,0 @@ - 1 1 -0.000000000000000 - 2 1 -0.000000000000000 - 2 2 -0.000000000000000 - 3 1 -0.050791929587912 - 3 2 -0.641172844324925 - 3 3 -0.000000000000000 - 4 1 0.000000000000000 - 4 2 0.000000000000000 - 4 3 0.000000000000000 - 4 4 -0.000000000000000 - 5 1 0.000000000000000 - 5 2 -0.000000000000000 - 5 3 -0.000000000000000 - 5 4 0.000000000000000 - 5 5 -0.000000000000000 - 6 1 -0.002229654052248 - 6 2 -0.262742503532769 - 6 3 -0.437630646182039 - 6 4 -0.147399448800486 - 6 5 0.000000000000000 - 6 6 -1.638036840407314 - 7 1 0.002229654052248 - 7 2 0.262742503532769 - 7 3 -0.437630646182039 - 7 4 0.147399448800486 - 7 5 -0.000000000000000 - 7 6 0.000000000000000 - 7 7 1.638036840407314 diff --git a/Project#12/input/h2o/STO-3G/muy.dat b/Project#12/input/h2o/STO-3G/muy.dat deleted file mode 100644 index 1efcbad..0000000 --- a/Project#12/input/h2o/STO-3G/muy.dat +++ /dev/null @@ -1,28 +0,0 @@ - 1 1 0.143225816551918 - 2 1 0.033902114587819 - 2 2 0.143225816551918 - 3 1 -0.000000000000000 - 3 2 0.000000000000000 - 3 3 0.143225816551918 - 4 1 -0.050791929587912 - 4 2 -0.641172844324925 - 4 3 -0.000000000000000 - 4 4 0.143225816551918 - 5 1 -0.000000000000000 - 5 2 0.000000000000000 - 5 3 0.000000000000000 - 5 4 -0.000000000000000 - 5 5 0.143225816551918 - 6 1 0.003758676726377 - 6 2 -0.149971890752635 - 6 3 -0.108952162150434 - 6 4 -0.334090713364948 - 6 5 0.000000000000000 - 6 6 -1.136548822546795 - 7 1 0.003758676726377 - 7 2 -0.149971890752635 - 7 3 0.108952162150434 - 7 4 -0.334090713364948 - 7 5 0.000000000000000 - 7 6 -0.206578984758302 - 7 7 -1.136548822546794 diff --git a/Project#12/input/h2o/STO-3G/muz.dat b/Project#12/input/h2o/STO-3G/muz.dat deleted file mode 100644 index 35dfd9f..0000000 --- a/Project#12/input/h2o/STO-3G/muz.dat +++ /dev/null @@ -1,28 +0,0 @@ - 1 1 -0.000000000000000 - 2 1 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-9.875876065926128 - 6 1 -1.231685872788711 - 6 2 -2.977227202971528 - 6 3 -1.822241058022723 - 6 4 -1.471788274313766 - 6 5 0.000000000000000 - 6 6 -5.300202953839792 - 7 1 -1.231685872788712 - 7 2 -2.977227202971529 - 7 3 1.822241058022724 - 7 4 -1.471788274313766 - 7 5 0.000000000000001 - 7 6 -1.067166014696110 - 7 7 -5.300202953839793 diff --git a/Project#12/output/ch4/STO-3G/output_cis.txt b/Project#12/output/ch4/STO-3G/output_cis.txt deleted file mode 100644 index f3c7774..0000000 --- a/Project#12/output/ch4/STO-3G/output_cis.txt +++ /dev/null @@ -1,83 +0,0 @@ -CIS Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 0.6020603967 16.3826654551 - 1 0.6020603967 16.3826654551 - 2 0.6020603967 16.3826654551 - 3 0.6546366260 17.8133172292 - 4 0.6546366260 17.8133172292 - 5 0.6546366260 17.8133172292 - 6 0.6546366260 17.8133172292 - 7 0.6546366260 17.8133172292 - 8 0.6546366260 17.8133172292 - 9 0.6546366260 17.8133172292 -10 0.6546366260 17.8133172292 -11 0.6546366260 17.8133172292 -12 0.7925534416 21.5661717003 -13 0.7925534416 21.5661717003 -14 0.7925534416 21.5661717003 -15 0.7925534416 21.5661717003 -16 0.7925534416 21.5661717003 -17 0.7925534416 21.5661717003 -18 0.8104989266 22.0544862905 -19 0.8104989266 22.0544862905 -20 0.8104989266 22.0544862905 -21 0.8104989266 22.0544862905 -22 0.8104989266 22.0544862905 -23 0.8104989266 22.0544862905 -24 0.8104989266 22.0544862905 -25 0.8104989266 22.0544862905 -26 0.8104989266 22.0544862905 -27 0.8170915540 22.2338782755 -28 0.8170915540 22.2338782755 -29 0.8170915540 22.2338782755 -30 0.8360459590 22.7496465909 -31 0.8360459590 22.7496465909 -32 0.8486146550 23.0916533779 -33 0.8486146550 23.0916533779 -34 0.8486146550 23.0916533779 -35 0.8486146550 23.0916533779 -36 0.8486146550 23.0916533779 -37 0.8486146550 23.0916533779 -38 0.8486146550 23.0916533779 -39 0.8486146550 23.0916533779 -40 0.8486146550 23.0916533779 -41 0.8913704032 24.2550800412 -42 0.8913704032 24.2550800412 -43 0.8913704032 24.2550800412 -44 0.9136371036 24.8609792263 -45 0.9136371036 24.8609792263 -46 0.9136371036 24.8609792263 -47 1.0550274759 28.7083526472 -48 1.1630382205 31.6474330168 -49 1.1630382205 31.6474330168 -50 1.1630382205 31.6474330168 -51 1.1630382205 31.6474330168 -52 1.1630382205 31.6474330168 -53 1.1630382205 31.6474330168 -54 1.1630382205 31.6474330168 -55 1.1630382205 31.6474330168 -56 1.1630382205 31.6474330168 -57 1.2328669461 33.5475424711 -58 1.2328669461 33.5475424711 -59 1.2328669461 33.5475424711 -60 1.2450464833 33.8789598567 -61 1.2450464833 33.8789598567 -62 1.2450464833 33.8789598567 -63 1.3671423280 37.2013098866 -64 11.0153873178 299.7397043034 -65 11.0153873178 299.7397043034 -66 11.0153873178 299.7397043034 -67 11.0153873178 299.7397043034 -68 11.0153873178 299.7397043034 -69 11.0153873178 299.7397043034 -70 11.0153873178 299.7397043034 -71 11.0153873178 299.7397043034 -72 11.0153873178 299.7397043034 -73 11.0571105649 300.8750355807 -74 11.0571105649 300.8750355807 -75 11.0571105649 300.8750355807 -76 11.0919527271 301.8231256577 -77 11.0919527271 301.8231256577 -78 11.0919527271 301.8231256577 -79 11.1922772144 304.5530552801 diff --git a/Project#12/output/ch4/STO-3G/output_rpa1.txt b/Project#12/output/ch4/STO-3G/output_rpa1.txt deleted file mode 100644 index 1280a2e..0000000 --- a/Project#12/output/ch4/STO-3G/output_rpa1.txt +++ /dev/null @@ -1,163 +0,0 @@ -RPA Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 -11.1920443899 -304.5467198931 - 1 -11.0918058048 -301.8191277536 - 2 -11.0918058048 -301.8191277536 - 3 -11.0918058048 -301.8191277536 - 4 -11.0570161273 -300.8724658402 - 5 -11.0570161273 -300.8724658402 - 6 -11.0570161273 -300.8724658402 - 7 -11.0153437688 -299.7385192922 - 8 -11.0153437688 -299.7385192922 - 9 -11.0153437688 -299.7385192922 -10 -11.0153437688 -299.7385192922 -11 -11.0153437688 -299.7385192922 -12 -11.0153437688 -299.7385192922 -13 -11.0153437688 -299.7385192922 -14 -11.0153437688 -299.7385192922 -15 -11.0153437688 -299.7385192922 -16 -1.3413754999 -36.5001687275 -17 -1.2436343096 -33.8405331976 -18 -1.2436343096 -33.8405331976 -19 -1.2436343096 -33.8405331976 -20 -1.2319714851 -33.5231760824 -21 -1.2319714851 -33.5231760824 -22 -1.2319714851 -33.5231760824 -23 -1.1611159110 -31.5951250540 -24 -1.1611159110 -31.5951250540 -25 -1.1611159110 -31.5951250540 -26 -1.1611159110 -31.5951250540 -27 -1.1611159110 -31.5951250540 -28 -1.1611159110 -31.5951250540 -29 -1.1611159110 -31.5951250540 -30 -1.1611159110 -31.5951250540 -31 -1.1611159110 -31.5951250540 -32 -1.0250451839 -27.8925044984 -33 -0.9131485984 -24.8476865100 -34 -0.9131485984 -24.8476865100 -35 -0.9131485984 -24.8476865100 -36 -0.8859617574 -24.1079053817 -37 -0.8859617574 -24.1079053817 -38 -0.8859617574 -24.1079053817 -39 -0.8454699509 -23.0060828334 -40 -0.8454699509 -23.0060828334 -41 -0.8454699509 -23.0060828334 -42 -0.8454699509 -23.0060828334 -43 -0.8454699509 -23.0060828334 -44 -0.8454699509 -23.0060828334 -45 -0.8454699509 -23.0060828334 -46 -0.8454699509 -23.0060828334 -47 -0.8454699509 -23.0060828334 -48 -0.8360443539 -22.7496029142 -49 -0.8360443539 -22.7496029142 -50 -0.8167562952 -22.2247555485 -51 -0.8167562952 -22.2247555485 -52 -0.8167562952 -22.2247555485 -53 -0.8103245505 -22.0497413444 -54 -0.8103245505 -22.0497413444 -55 -0.8103245505 -22.0497413444 -56 -0.8103245505 -22.0497413444 -57 -0.8103245505 -22.0497413444 -58 -0.8103245505 -22.0497413444 -59 -0.8103245505 -22.0497413444 -60 -0.8103245505 -22.0497413444 -61 -0.8103245505 -22.0497413444 -62 -0.7914475213 -21.5360785018 -63 -0.7914475213 -21.5360785018 -64 -0.7914475213 -21.5360785018 -65 -0.7914475213 -21.5360785018 -66 -0.7914475213 -21.5360785018 -67 -0.7914475213 -21.5360785018 -68 -0.6390526798 -17.3892624692 -69 -0.6390526798 -17.3892624692 -70 -0.6390526798 -17.3892624692 -71 -0.6390526798 -17.3892624692 -72 -0.6390526798 -17.3892624692 -73 -0.6390526798 -17.3892624692 -74 -0.6390526798 -17.3892624692 -75 -0.6390526798 -17.3892624692 -76 -0.6390526798 -17.3892624692 -77 -0.5656719613 -15.3924997386 -78 -0.5656719613 -15.3924997386 -79 -0.5656719613 -15.3924997386 -80 0.5656719613 15.3924997386 -81 0.5656719613 15.3924997386 -82 0.5656719613 15.3924997386 -83 0.6390526798 17.3892624692 -84 0.6390526798 17.3892624692 -85 0.6390526798 17.3892624692 -86 0.6390526798 17.3892624692 -87 0.6390526798 17.3892624692 -88 0.6390526798 17.3892624692 -89 0.6390526798 17.3892624692 -90 0.6390526798 17.3892624692 -91 0.6390526798 17.3892624692 -92 0.7914475213 21.5360785018 -93 0.7914475213 21.5360785018 -94 0.7914475213 21.5360785018 -95 0.7914475213 21.5360785018 -96 0.7914475213 21.5360785018 -97 0.7914475213 21.5360785018 -98 0.8103245505 22.0497413444 -99 0.8103245505 22.0497413444 -100 0.8103245505 22.0497413444 -101 0.8103245505 22.0497413444 -102 0.8103245505 22.0497413444 -103 0.8103245505 22.0497413444 -104 0.8103245505 22.0497413444 -105 0.8103245505 22.0497413444 -106 0.8103245505 22.0497413444 -107 0.8167562952 22.2247555485 -108 0.8167562952 22.2247555485 -109 0.8167562952 22.2247555485 -110 0.8360443539 22.7496029142 -111 0.8360443539 22.7496029142 -112 0.8454699509 23.0060828334 -113 0.8454699509 23.0060828334 -114 0.8454699509 23.0060828334 -115 0.8454699509 23.0060828334 -116 0.8454699509 23.0060828334 -117 0.8454699509 23.0060828334 -118 0.8454699509 23.0060828334 -119 0.8454699509 23.0060828334 -120 0.8454699509 23.0060828334 -121 0.8859617574 24.1079053817 -122 0.8859617574 24.1079053817 -123 0.8859617574 24.1079053817 -124 0.9131485984 24.8476865100 -125 0.9131485984 24.8476865100 -126 0.9131485984 24.8476865100 -127 1.0250451839 27.8925044984 -128 1.1611159110 31.5951250540 -129 1.1611159110 31.5951250540 -130 1.1611159110 31.5951250540 -131 1.1611159110 31.5951250540 -132 1.1611159110 31.5951250540 -133 1.1611159110 31.5951250540 -134 1.1611159110 31.5951250540 -135 1.1611159110 31.5951250540 -136 1.1611159110 31.5951250540 -137 1.2319714851 33.5231760824 -138 1.2319714851 33.5231760824 -139 1.2319714851 33.5231760824 -140 1.2436343096 33.8405331976 -141 1.2436343096 33.8405331976 -142 1.2436343096 33.8405331976 -143 1.3413754999 36.5001687275 -144 11.0153437688 299.7385192922 -145 11.0153437688 299.7385192922 -146 11.0153437688 299.7385192922 -147 11.0153437688 299.7385192922 -148 11.0153437688 299.7385192922 -149 11.0153437688 299.7385192922 -150 11.0153437688 299.7385192922 -151 11.0153437688 299.7385192922 -152 11.0153437688 299.7385192922 -153 11.0570161273 300.8724658402 -154 11.0570161273 300.8724658402 -155 11.0570161273 300.8724658402 -156 11.0918058048 301.8191277536 -157 11.0918058048 301.8191277536 -158 11.0918058048 301.8191277536 -159 11.1920443899 304.5467198931 diff --git a/Project#12/output/ch4/STO-3G/output_rpa2.txt b/Project#12/output/ch4/STO-3G/output_rpa2.txt deleted file mode 100644 index a4d4ada..0000000 --- a/Project#12/output/ch4/STO-3G/output_rpa2.txt +++ /dev/null @@ -1,83 +0,0 @@ -RPA Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 0.5656719613 15.3924997386 - 1 0.5656719613 15.3924997386 - 2 0.5656719613 15.3924997386 - 3 0.6390526798 17.3892624692 - 4 0.6390526798 17.3892624692 - 5 0.6390526798 17.3892624692 - 6 0.6390526798 17.3892624692 - 7 0.6390526798 17.3892624692 - 8 0.6390526798 17.3892624692 - 9 0.6390526798 17.3892624692 -10 0.6390526798 17.3892624692 -11 0.6390526798 17.3892624692 -12 0.7914475213 21.5360785018 -13 0.7914475213 21.5360785018 -14 0.7914475213 21.5360785018 -15 0.7914475213 21.5360785018 -16 0.7914475213 21.5360785018 -17 0.7914475213 21.5360785018 -18 0.8103245505 22.0497413444 -19 0.8103245505 22.0497413444 -20 0.8103245505 22.0497413444 -21 0.8103245505 22.0497413444 -22 0.8103245505 22.0497413444 -23 0.8103245505 22.0497413444 -24 0.8103245505 22.0497413444 -25 0.8103245505 22.0497413444 -26 0.8103245505 22.0497413444 -27 0.8167562952 22.2247555485 -28 0.8167562952 22.2247555485 -29 0.8167562952 22.2247555485 -30 0.8360443539 22.7496029142 -31 0.8360443539 22.7496029142 -32 0.8454699509 23.0060828334 -33 0.8454699509 23.0060828334 -34 0.8454699509 23.0060828334 -35 0.8454699509 23.0060828334 -36 0.8454699509 23.0060828334 -37 0.8454699509 23.0060828334 -38 0.8454699509 23.0060828334 -39 0.8454699509 23.0060828334 -40 0.8454699509 23.0060828334 -41 0.8859617574 24.1079053817 -42 0.8859617574 24.1079053817 -43 0.8859617574 24.1079053817 -44 0.9131485984 24.8476865100 -45 0.9131485984 24.8476865100 -46 0.9131485984 24.8476865100 -47 1.0250451839 27.8925044984 -48 1.1611159110 31.5951250540 -49 1.1611159110 31.5951250540 -50 1.1611159110 31.5951250540 -51 1.1611159110 31.5951250540 -52 1.1611159110 31.5951250540 -53 1.1611159110 31.5951250540 -54 1.1611159110 31.5951250540 -55 1.1611159110 31.5951250540 -56 1.1611159110 31.5951250540 -57 1.2319714851 33.5231760824 -58 1.2319714851 33.5231760824 -59 1.2319714851 33.5231760824 -60 1.2436343096 33.8405331976 -61 1.2436343096 33.8405331976 -62 1.2436343096 33.8405331976 -63 1.3413754999 36.5001687275 -64 11.0153437688 299.7385192922 -65 11.0153437688 299.7385192922 -66 11.0153437688 299.7385192922 -67 11.0153437688 299.7385192922 -68 11.0153437688 299.7385192922 -69 11.0153437688 299.7385192922 -70 11.0153437688 299.7385192922 -71 11.0153437688 299.7385192922 -72 11.0153437688 299.7385192922 -73 11.0570161273 300.8724658402 -74 11.0570161273 300.8724658402 -75 11.0570161273 300.8724658402 -76 11.0918058048 301.8191277536 -77 11.0918058048 301.8191277536 -78 11.0918058048 301.8191277536 -79 11.1920443899 304.5467198931 diff --git a/Project#12/output/h2o/DZ/output_cis.txt b/Project#12/output/h2o/DZ/output_cis.txt deleted file mode 100644 index 9be5a85..0000000 --- a/Project#12/output/h2o/DZ/output_cis.txt +++ /dev/null @@ -1,183 +0,0 @@ -CIS Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 0.2521733734 6.8618896640 - 1 0.2521733734 6.8618896640 - 2 0.2521733734 6.8618896640 - 3 0.2929742879 7.9721233473 - 4 0.2951406202 8.0310714157 - 5 0.2951406202 8.0310714157 - 6 0.2951406202 8.0310714157 - 7 0.3175855602 8.6418206778 - 8 0.3175855602 8.6418206778 - 9 0.3175855602 8.6418206778 -10 0.3372543633 9.1770284804 -11 0.3372543633 9.1770284804 -12 0.3372543633 9.1770284804 -13 0.3466019985 9.4313869817 -14 0.3844210667 10.4604816447 -15 0.4129756328 11.2374799430 -16 0.4129756328 11.2374799430 -17 0.4129756328 11.2374799430 -18 0.4382472054 11.9251447065 -19 0.4482402900 12.1970665300 -20 0.4482402900 12.1970665300 -21 0.4482402900 12.1970665300 -22 0.4912333948 13.3669519050 -23 0.6128418167 16.6760386748 -24 0.7609972870 20.7074971761 -25 0.7609972870 20.7074971761 -26 0.7609972870 20.7074971761 -27 0.8535911371 23.2270684304 -28 0.8535911371 23.2270684304 -29 0.8535911371 23.2270684304 -30 0.8889605749 24.1895062030 -31 0.8889605749 24.1895062030 -32 0.8889605749 24.1895062030 -33 0.8997293379 24.4825350145 -34 0.9172227314 24.9585477444 -35 0.9172227314 24.9585477444 -36 0.9172227314 24.9585477444 -37 0.9196035320 25.0233317080 -38 0.9360622484 25.4711898419 -39 0.9900913436 26.9413755497 -40 0.9900913436 26.9413755497 -41 0.9900913436 26.9413755497 -42 1.0196639079 27.7460745986 -43 1.0208291454 27.7777818755 -44 1.0208291454 27.7777818755 -45 1.0208291454 27.7777818755 -46 1.0430134724 28.3814395988 -47 1.0430134724 28.3814395988 -48 1.0430134724 28.3814395988 -49 1.0435205825 28.3952385717 -50 1.0435205825 28.3952385717 -51 1.0435205825 28.3952385717 -52 1.0589333138 28.8146344020 -53 1.0683904166 29.0719716263 -54 1.0683904166 29.0719716263 -55 1.0683904166 29.0719716263 -56 1.0818224247 29.4374699991 -57 1.0839995034 29.4967104871 -58 1.0966958636 29.8421911455 -59 1.0966958636 29.8421911455 -60 1.0966958636 29.8421911455 -61 1.1045376485 30.0555739526 -62 1.1429095637 31.0997121382 -63 1.1429095637 31.0997121382 -64 1.1429095637 31.0997121382 -65 1.1608423912 31.5876823081 -66 1.1775553491 32.0424586042 -67 1.1788725973 32.0783022447 -68 1.1788725973 32.0783022447 -69 1.1788725973 32.0783022447 -70 1.1802547539 32.1159121075 -71 1.1802547539 32.1159121075 -72 1.1802547539 32.1159121075 -73 1.1864214248 32.2837133897 -74 1.1864214248 32.2837133897 -75 1.1864214248 32.2837133897 -76 1.1909275267 32.4063289287 -77 1.1909275267 32.4063289287 -78 1.1909275267 32.4063289287 -79 1.1992870889 32.6338009765 -80 1.2050152370 32.7896696142 -81 1.2709419806 34.5836022352 -82 1.2848927574 34.9632168220 -83 1.3025867791 35.4446888472 -84 1.3025867791 35.4446888472 -85 1.3025867791 35.4446888472 -86 1.3048104001 35.5051957978 -87 1.3048104001 35.5051957978 -88 1.3048104001 35.5051957978 -89 1.3417929903 36.5115290592 -90 1.3923912294 37.8883577436 -91 1.5015207444 40.8578809749 -92 1.5015207444 40.8578809749 -93 1.5015207444 40.8578809749 -94 1.5616570378 42.4942496566 -95 1.5998835670 43.5344317423 -96 1.5998835670 43.5344317423 -97 1.5998835670 43.5344317423 -98 1.6300924841 44.3564465842 -99 1.6704631674 45.4549732468 -100 1.6704631674 45.4549732468 -101 1.6704631674 45.4549732468 -102 1.6958618077 46.1460956502 -103 1.7053891289 46.4053435871 -104 1.7086903159 46.4951721852 -105 1.7086903159 46.4951721852 -106 1.7086903159 46.4951721852 -107 1.7193962928 46.7864925240 -108 1.7193962928 46.7864925240 -109 1.7193962928 46.7864925240 -110 1.7468949648 47.5347588865 -111 1.7961825415 48.8759231365 -112 1.8400659925 50.0700357220 -113 1.8400659925 50.0700357220 -114 1.8400659925 50.0700357220 -115 1.8494445167 50.3252347434 -116 1.9514915021 53.1020352633 -117 1.9514915021 53.1020352633 -118 1.9514915021 53.1020352633 -119 1.9585941005 53.2953040681 -120 1.9585941005 53.2953040681 -121 1.9585941005 53.2953040681 -122 1.9917036399 54.1962477462 -123 2.0074584888 54.6249529382 -124 2.3516024228 63.9894535262 -125 2.3516024228 63.9894535262 -126 2.3516024228 63.9894535262 -127 2.5263164705 68.7435974778 -128 20.1084697150 547.1715694156 -129 20.1084697150 547.1715694156 -130 20.1084697150 547.1715694157 -131 20.1305581439 547.7726176525 -132 20.1305581439 547.7726176525 -133 20.1305581439 547.7726176525 -134 20.1816860796 549.1638599127 -135 20.1966475761 549.5709771932 -136 20.6192732718 561.0710450002 -137 20.6192732718 561.0710450002 -138 20.6192732718 561.0710450002 -139 20.6893822816 562.9787812645 -140 20.6971416072 563.1899202742 -141 20.6971416072 563.1899202742 -142 20.6971416072 563.1899202742 -143 20.7607281783 564.9201744587 -144 20.9086141773 568.9443003799 -145 20.9086141774 568.9443003799 -146 20.9086141774 568.9443003799 -147 20.9424972822 569.8662935459 -148 21.1527546189 575.5876059353 -149 21.1527546189 575.5876059353 -150 21.1527546189 575.5876059353 -151 21.2060372982 577.0374809219 -152 21.2280545565 577.6365925365 -153 21.2280545565 577.6365925365 -154 21.2280545565 577.6365925365 -155 21.2302688438 577.6968455089 -156 21.4390500146 583.3779899485 -157 21.4390500146 583.3779899485 -158 21.4390500146 583.3779899485 -159 21.5218168832 585.6301592092 -160 42.7621675206 1163.6013404027 -161 42.7621675206 1163.6013404027 -162 42.7621675206 1163.6013404027 -163 42.7981247678 1164.5797730579 -164 42.8862296564 1166.9771951816 -165 42.8862296564 1166.9771951816 -166 42.8862296564 1166.9771951816 -167 42.9403208398 1168.4490703731 -168 43.1142392043 1173.1815629870 -169 43.1142392043 1173.1815629870 -170 43.1142392043 1173.1815629870 -171 43.1360530999 1173.7751409015 -172 43.5523870698 1185.1040045561 -173 43.5523870698 1185.1040045561 -174 43.5523870698 1185.1040045561 -175 43.6857362455 1188.7325689762 -176 59.3944139114 1616.1813969429 -177 59.3944139114 1616.1813969429 -178 59.3944139114 1616.1813969429 -179 61.4997435704 1673.4695222945 diff --git a/Project#12/output/h2o/DZ/output_rpa1.txt b/Project#12/output/h2o/DZ/output_rpa1.txt deleted file mode 100644 index e8037c6..0000000 --- a/Project#12/output/h2o/DZ/output_rpa1.txt +++ /dev/null @@ -1,363 +0,0 @@ -RPA Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 -61.4891345044 -1673.1808389998 - 1 -59.3835794777 -1615.8865811678 - 2 -59.3835794777 -1615.8865811678 - 3 -59.3835794777 -1615.8865811678 - 4 -43.6850527055 -1188.7139691694 - 5 -43.5517652522 -1185.0870842781 - 6 -43.5517652522 -1185.0870842781 - 7 -43.5517652522 -1185.0870842781 - 8 -43.1360187270 -1173.7742055813 - 9 -43.1142285714 -1173.1812736557 -10 -43.1142285714 -1173.1812736557 -11 -43.1142285714 -1173.1812736557 -12 -42.9401448873 -1168.4442825278 -13 -42.8860510290 -1166.9723345503 -14 -42.8860510290 -1166.9723345503 -15 -42.8860510290 -1166.9723345503 -16 -42.7980840912 -1164.5786662060 -17 -42.7621525954 -1163.6009342744 -18 -42.7621525954 -1163.6009342744 -19 -42.7621525954 -1163.6009342744 -20 -21.5210414842 -585.6090598276 -21 -21.4385839521 -583.3653079218 -22 -21.4385839521 -583.3653079218 -23 -21.4385839521 -583.3653079218 -24 -21.2302607735 -577.6966259084 -25 -21.2280501556 -577.6364727843 -26 -21.2280501556 -577.6364727843 -27 -21.2280501556 -577.6364727843 -28 -21.2057111961 -577.0286073580 -29 -21.1522912000 -575.5749958436 -30 -21.1522912000 -575.5749958436 -31 -21.1522912000 -575.5749958436 -32 -20.9424014458 -569.8636857426 -33 -20.9085871992 -568.9435662784 -34 -20.9085871992 -568.9435662784 -35 -20.9085871992 -568.9435662784 -36 -20.7605069175 -564.9141537329 -37 -20.6969385212 -563.1843940993 -38 -20.6969385212 -563.1843940993 -39 -20.6969385212 -563.1843940993 -40 -20.6891875564 -562.9734825971 -41 -20.6192195219 -561.0695824114 -42 -20.6192195219 -561.0695824114 -43 -20.6192195219 -561.0695824114 -44 -20.1964961770 -549.5668574711 -45 -20.1813433999 -549.1545352538 -46 -20.1304669012 -547.7701348498 -47 -20.1304669012 -547.7701348498 -48 -20.1304669012 -547.7701348498 -49 -20.1081729795 -547.1634949464 -50 -20.1081729795 -547.1634949464 -51 -20.1081729795 -547.1634949464 -52 -2.4912180490 -67.7885343310 -53 -2.3495377688 -63.9332722255 -54 -2.3495377688 -63.9332722255 -55 -2.3495377688 -63.9332722255 -56 -1.9967810945 -54.3344103626 -57 -1.9909510815 -54.1757698794 -58 -1.9580240090 -53.2797913082 -59 -1.9580240090 -53.2797913082 -60 -1.9580240090 -53.2797913082 -61 -1.9507087396 -53.0807355128 -62 -1.9507087396 -53.0807355128 -63 -1.9507087396 -53.0807355128 -64 -1.8484993758 -50.2995165143 -65 -1.8389879536 -50.0407012066 -66 -1.8389879536 -50.0407012066 -67 -1.8389879536 -50.0407012066 -68 -1.7955533375 -48.8588018657 -69 -1.7408572152 -47.3704656834 -70 -1.7178946274 -46.7456307049 -71 -1.7178946274 -46.7456307049 -72 -1.7178946274 -46.7456307049 -73 -1.7052295875 -46.4010023058 -74 -1.7052295875 -46.4010023058 -75 -1.7052295875 -46.4010023058 -76 -1.6982326585 -46.2106088698 -77 -1.6942859733 -46.1032156199 -78 -1.6681323047 -45.3915481419 -79 -1.6681323047 -45.3915481419 -80 -1.6681323047 -45.3915481419 -81 -1.6296345685 -44.3439862434 -82 -1.5957624529 -43.4222921055 -83 -1.5957624529 -43.4222921055 -84 -1.5957624529 -43.4222921055 -85 -1.4952406969 -40.6869946041 -86 -1.4952406969 -40.6869946041 -87 -1.4952406969 -40.6869946041 -88 -1.4807532727 -40.2927773043 -89 -1.3863510746 -37.7239990909 -90 -1.3272879981 -36.1168337167 -91 -1.3039411132 -35.4815416313 -92 -1.3039411132 -35.4815416313 -93 -1.3039411132 -35.4815416313 -94 -1.3010908534 -35.4039832107 -95 -1.3010908534 -35.4039832107 -96 -1.3010908534 -35.4039832107 -97 -1.2835315942 -34.9261782094 -98 -1.2699369794 -34.5562551452 -99 -1.2047405229 -32.7821943681 -100 -1.1990338349 -32.6269096825 -101 -1.1905863148 -32.3970442108 -102 -1.1905863148 -32.3970442108 -103 -1.1905863148 -32.3970442108 -104 -1.1814597603 -32.1487015362 -105 -1.1814597603 -32.1487015362 -106 -1.1814597603 -32.1487015362 -107 -1.1792733838 -32.0892080464 -108 -1.1792733838 -32.0892080464 -109 -1.1792733838 -32.0892080464 -110 -1.1758327222 -31.9955842029 -111 -1.1753092211 -31.9813392152 -112 -1.1753092211 -31.9813392152 -113 -1.1753092211 -31.9813392152 -114 -1.1475558667 -31.2261426891 -115 -1.1388720042 -30.9898461062 -116 -1.1388720042 -30.9898461062 -117 -1.1388720042 -30.9898461062 -118 -1.1017288367 -29.9791433743 -119 -1.0910548099 -29.6886924329 -120 -1.0910548099 -29.6886924329 -121 -1.0910548099 -29.6886924329 -122 -1.0798335665 -29.3833511768 -123 -1.0791284900 -29.3641653409 -124 -1.0609414821 -28.8692786707 -125 -1.0609414821 -28.8692786707 -126 -1.0609414821 -28.8692786707 -127 -1.0543861132 -28.6909005273 -128 -1.0398010420 -28.2940261545 -129 -1.0398010420 -28.2940261545 -130 -1.0398010420 -28.2940261545 -131 -1.0363872957 -28.2011347046 -132 -1.0363872957 -28.2011347046 -133 -1.0363872957 -28.2011347046 -134 -1.0183208743 -27.7095293104 -135 -1.0142892498 -27.5998247752 -136 -1.0142892498 -27.5998247752 -137 -1.0142892498 -27.5998247752 -138 -0.9861547467 -26.8342568122 -139 -0.9861547467 -26.8342568122 -140 -0.9861547467 -26.8342568122 -141 -0.9315745593 -25.3490753336 -142 -0.9147647449 -24.8916634733 -143 -0.9116099455 -24.8058182263 -144 -0.9116099455 -24.8058182263 -145 -0.9116099455 -24.8058182263 -146 -0.8967505042 -24.4014779697 -147 -0.8789143569 -23.9161385664 -148 -0.8789143569 -23.9161385664 -149 -0.8789143569 -23.9161385664 -150 -0.8453707737 -23.0033841229 -151 -0.8453707737 -23.0033841229 -152 -0.8453707737 -23.0033841229 -153 -0.7432112818 -20.2235221897 -154 -0.7432112818 -20.2235221897 -155 -0.7432112818 -20.2235221897 -156 -0.6008413336 -16.3494935283 -157 -0.4873207212 -13.2604841437 -158 -0.4334070450 -11.7934391018 -159 -0.4284475765 -11.6584870029 -160 -0.4284475765 -11.6584870029 -161 -0.4284475765 -11.6584870029 -162 -0.4070382580 -11.0759180378 -163 -0.4070382580 -11.0759180378 -164 -0.4070382580 -11.0759180378 -165 -0.3800739542 -10.3421923684 -166 -0.3427717403 -9.3271618244 -167 -0.3111679098 -8.4671899948 -168 -0.3111679098 -8.4671899948 -169 -0.3111679098 -8.4671899948 -170 -0.3073528488 -8.3633783674 -171 -0.3073528488 -8.3633783674 -172 -0.3073528488 -8.3633783674 -173 -0.2896457262 -7.8815498545 -174 -0.2637567614 -7.1770852349 -175 -0.2637567614 -7.1770852349 -176 -0.2637567614 -7.1770852349 -177 -0.2458308730 -6.6893038844 -178 -0.2458308730 -6.6893038844 -179 -0.2458308730 -6.6893038844 -180 0.2458308730 6.6893038844 -181 0.2458308730 6.6893038844 -182 0.2458308730 6.6893038844 -183 0.2637567614 7.1770852349 -184 0.2637567614 7.1770852349 -185 0.2637567614 7.1770852349 -186 0.2896457262 7.8815498545 -187 0.3073528488 8.3633783674 -188 0.3073528488 8.3633783674 -189 0.3073528488 8.3633783674 -190 0.3111679098 8.4671899948 -191 0.3111679098 8.4671899948 -192 0.3111679098 8.4671899948 -193 0.3427717403 9.3271618244 -194 0.3800739542 10.3421923684 -195 0.4070382580 11.0759180378 -196 0.4070382580 11.0759180378 -197 0.4070382580 11.0759180378 -198 0.4284475765 11.6584870029 -199 0.4284475765 11.6584870029 -200 0.4284475765 11.6584870029 -201 0.4334070450 11.7934391018 -202 0.4873207212 13.2604841437 -203 0.6008413336 16.3494935283 -204 0.7432112818 20.2235221897 -205 0.7432112818 20.2235221897 -206 0.7432112818 20.2235221897 -207 0.8453707737 23.0033841229 -208 0.8453707737 23.0033841229 -209 0.8453707737 23.0033841229 -210 0.8789143569 23.9161385664 -211 0.8789143569 23.9161385664 -212 0.8789143569 23.9161385664 -213 0.8967505042 24.4014779697 -214 0.9116099455 24.8058182263 -215 0.9116099455 24.8058182263 -216 0.9116099455 24.8058182263 -217 0.9147647449 24.8916634733 -218 0.9315745593 25.3490753336 -219 0.9861547467 26.8342568122 -220 0.9861547467 26.8342568122 -221 0.9861547467 26.8342568122 -222 1.0142892498 27.5998247752 -223 1.0142892498 27.5998247752 -224 1.0142892498 27.5998247752 -225 1.0183208743 27.7095293104 -226 1.0363872957 28.2011347046 -227 1.0363872957 28.2011347046 -228 1.0363872957 28.2011347046 -229 1.0398010420 28.2940261545 -230 1.0398010420 28.2940261545 -231 1.0398010420 28.2940261545 -232 1.0543861132 28.6909005273 -233 1.0609414821 28.8692786707 -234 1.0609414821 28.8692786707 -235 1.0609414821 28.8692786707 -236 1.0791284900 29.3641653409 -237 1.0798335665 29.3833511768 -238 1.0910548099 29.6886924329 -239 1.0910548099 29.6886924329 -240 1.0910548099 29.6886924329 -241 1.1017288367 29.9791433743 -242 1.1388720042 30.9898461062 -243 1.1388720042 30.9898461062 -244 1.1388720042 30.9898461062 -245 1.1475558667 31.2261426891 -246 1.1753092211 31.9813392152 -247 1.1753092211 31.9813392152 -248 1.1753092211 31.9813392152 -249 1.1758327222 31.9955842029 -250 1.1792733838 32.0892080464 -251 1.1792733838 32.0892080464 -252 1.1792733838 32.0892080464 -253 1.1814597603 32.1487015362 -254 1.1814597603 32.1487015362 -255 1.1814597603 32.1487015362 -256 1.1905863148 32.3970442108 -257 1.1905863148 32.3970442108 -258 1.1905863148 32.3970442108 -259 1.1990338349 32.6269096825 -260 1.2047405229 32.7821943681 -261 1.2699369794 34.5562551452 -262 1.2835315942 34.9261782094 -263 1.3010908534 35.4039832107 -264 1.3010908534 35.4039832107 -265 1.3010908534 35.4039832107 -266 1.3039411132 35.4815416313 -267 1.3039411132 35.4815416313 -268 1.3039411132 35.4815416313 -269 1.3272879981 36.1168337167 -270 1.3863510746 37.7239990909 -271 1.4807532727 40.2927773043 -272 1.4952406969 40.6869946041 -273 1.4952406969 40.6869946041 -274 1.4952406969 40.6869946041 -275 1.5957624529 43.4222921055 -276 1.5957624529 43.4222921055 -277 1.5957624529 43.4222921055 -278 1.6296345685 44.3439862434 -279 1.6681323047 45.3915481419 -280 1.6681323047 45.3915481419 -281 1.6681323047 45.3915481419 -282 1.6942859733 46.1032156199 -283 1.6982326585 46.2106088698 -284 1.7052295875 46.4010023058 -285 1.7052295875 46.4010023058 -286 1.7052295875 46.4010023058 -287 1.7178946274 46.7456307049 -288 1.7178946274 46.7456307049 -289 1.7178946274 46.7456307049 -290 1.7408572152 47.3704656834 -291 1.7955533375 48.8588018657 -292 1.8389879536 50.0407012066 -293 1.8389879536 50.0407012066 -294 1.8389879536 50.0407012066 -295 1.8484993758 50.2995165143 -296 1.9507087396 53.0807355128 -297 1.9507087396 53.0807355128 -298 1.9507087396 53.0807355128 -299 1.9580240090 53.2797913082 -300 1.9580240090 53.2797913082 -301 1.9580240090 53.2797913082 -302 1.9909510815 54.1757698794 -303 1.9967810945 54.3344103626 -304 2.3495377688 63.9332722255 -305 2.3495377688 63.9332722255 -306 2.3495377688 63.9332722255 -307 2.4912180490 67.7885343310 -308 20.1081729795 547.1634949464 -309 20.1081729795 547.1634949464 -310 20.1081729795 547.1634949464 -311 20.1304669012 547.7701348498 -312 20.1304669012 547.7701348498 -313 20.1304669012 547.7701348498 -314 20.1813433999 549.1545352538 -315 20.1964961770 549.5668574711 -316 20.6192195219 561.0695824114 -317 20.6192195219 561.0695824114 -318 20.6192195219 561.0695824114 -319 20.6891875564 562.9734825971 -320 20.6969385212 563.1843940993 -321 20.6969385212 563.1843940993 -322 20.6969385212 563.1843940993 -323 20.7605069175 564.9141537329 -324 20.9085871992 568.9435662784 -325 20.9085871992 568.9435662784 -326 20.9085871992 568.9435662784 -327 20.9424014458 569.8636857426 -328 21.1522912000 575.5749958436 -329 21.1522912000 575.5749958436 -330 21.1522912000 575.5749958436 -331 21.2057111961 577.0286073580 -332 21.2280501556 577.6364727843 -333 21.2280501556 577.6364727843 -334 21.2280501556 577.6364727843 -335 21.2302607735 577.6966259084 -336 21.4385839521 583.3653079218 -337 21.4385839521 583.3653079218 -338 21.4385839521 583.3653079218 -339 21.5210414842 585.6090598276 -340 42.7621525954 1163.6009342744 -341 42.7621525954 1163.6009342744 -342 42.7621525954 1163.6009342744 -343 42.7980840912 1164.5786662060 -344 42.8860510290 1166.9723345503 -345 42.8860510290 1166.9723345503 -346 42.8860510290 1166.9723345503 -347 42.9401448873 1168.4442825278 -348 43.1142285714 1173.1812736557 -349 43.1142285714 1173.1812736557 -350 43.1142285714 1173.1812736557 -351 43.1360187270 1173.7742055813 -352 43.5517652522 1185.0870842781 -353 43.5517652522 1185.0870842781 -354 43.5517652522 1185.0870842781 -355 43.6850527055 1188.7139691694 -356 59.3835794777 1615.8865811678 -357 59.3835794777 1615.8865811678 -358 59.3835794777 1615.8865811678 -359 61.4891345044 1673.1808389998 diff --git a/Project#12/output/h2o/DZ/output_rpa2.txt b/Project#12/output/h2o/DZ/output_rpa2.txt deleted file mode 100644 index 6453e50..0000000 --- a/Project#12/output/h2o/DZ/output_rpa2.txt +++ /dev/null @@ -1,183 +0,0 @@ -RPA Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 0.2458308730 6.6893038844 - 1 0.2458308730 6.6893038844 - 2 0.2458308730 6.6893038844 - 3 0.2637567614 7.1770852349 - 4 0.2637567614 7.1770852349 - 5 0.2637567614 7.1770852349 - 6 0.2896457262 7.8815498545 - 7 0.3073528488 8.3633783674 - 8 0.3073528488 8.3633783674 - 9 0.3073528488 8.3633783674 -10 0.3111679098 8.4671899948 -11 0.3111679098 8.4671899948 -12 0.3111679098 8.4671899948 -13 0.3427717403 9.3271618244 -14 0.3800739542 10.3421923684 -15 0.4070382580 11.0759180378 -16 0.4070382580 11.0759180378 -17 0.4070382580 11.0759180378 -18 0.4284475765 11.6584870029 -19 0.4284475765 11.6584870029 -20 0.4284475765 11.6584870029 -21 0.4334070450 11.7934391018 -22 0.4873207212 13.2604841437 -23 0.6008413336 16.3494935283 -24 0.7432112818 20.2235221897 -25 0.7432112818 20.2235221897 -26 0.7432112818 20.2235221897 -27 0.8453707737 23.0033841229 -28 0.8453707737 23.0033841229 -29 0.8453707737 23.0033841229 -30 0.8789143569 23.9161385664 -31 0.8789143569 23.9161385664 -32 0.8789143569 23.9161385664 -33 0.8967505042 24.4014779697 -34 0.9116099455 24.8058182263 -35 0.9116099455 24.8058182263 -36 0.9116099455 24.8058182263 -37 0.9147647449 24.8916634733 -38 0.9315745593 25.3490753336 -39 0.9861547467 26.8342568122 -40 0.9861547467 26.8342568122 -41 0.9861547467 26.8342568122 -42 1.0142892498 27.5998247752 -43 1.0142892498 27.5998247752 -44 1.0142892498 27.5998247752 -45 1.0183208743 27.7095293104 -46 1.0363872957 28.2011347046 -47 1.0363872957 28.2011347046 -48 1.0363872957 28.2011347046 -49 1.0398010420 28.2940261545 -50 1.0398010420 28.2940261545 -51 1.0398010420 28.2940261545 -52 1.0543861132 28.6909005273 -53 1.0609414821 28.8692786707 -54 1.0609414821 28.8692786707 -55 1.0609414821 28.8692786707 -56 1.0791284900 29.3641653410 -57 1.0798335665 29.3833511768 -58 1.0910548099 29.6886924329 -59 1.0910548099 29.6886924329 -60 1.0910548099 29.6886924329 -61 1.1017288367 29.9791433743 -62 1.1388720042 30.9898461062 -63 1.1388720042 30.9898461062 -64 1.1388720042 30.9898461062 -65 1.1475558667 31.2261426891 -66 1.1753092211 31.9813392152 -67 1.1753092211 31.9813392152 -68 1.1753092211 31.9813392152 -69 1.1758327222 31.9955842029 -70 1.1792733838 32.0892080464 -71 1.1792733838 32.0892080464 -72 1.1792733838 32.0892080464 -73 1.1814597603 32.1487015362 -74 1.1814597603 32.1487015362 -75 1.1814597603 32.1487015362 -76 1.1905863148 32.3970442108 -77 1.1905863148 32.3970442108 -78 1.1905863148 32.3970442108 -79 1.1990338349 32.6269096825 -80 1.2047405229 32.7821943681 -81 1.2699369794 34.5562551452 -82 1.2835315942 34.9261782094 -83 1.3010908534 35.4039832107 -84 1.3010908534 35.4039832107 -85 1.3010908534 35.4039832107 -86 1.3039411132 35.4815416313 -87 1.3039411132 35.4815416313 -88 1.3039411132 35.4815416313 -89 1.3272879981 36.1168337167 -90 1.3863510746 37.7239990909 -91 1.4807532727 40.2927773043 -92 1.4952406969 40.6869946041 -93 1.4952406969 40.6869946041 -94 1.4952406969 40.6869946041 -95 1.5957624529 43.4222921055 -96 1.5957624529 43.4222921055 -97 1.5957624529 43.4222921055 -98 1.6296345685 44.3439862434 -99 1.6681323047 45.3915481419 -100 1.6681323047 45.3915481419 -101 1.6681323047 45.3915481419 -102 1.6942859733 46.1032156199 -103 1.6982326585 46.2106088698 -104 1.7052295875 46.4010023058 -105 1.7052295875 46.4010023058 -106 1.7052295875 46.4010023058 -107 1.7178946274 46.7456307049 -108 1.7178946274 46.7456307049 -109 1.7178946274 46.7456307049 -110 1.7408572152 47.3704656834 -111 1.7955533375 48.8588018657 -112 1.8389879536 50.0407012066 -113 1.8389879536 50.0407012066 -114 1.8389879536 50.0407012066 -115 1.8484993758 50.2995165143 -116 1.9507087396 53.0807355128 -117 1.9507087396 53.0807355128 -118 1.9507087396 53.0807355128 -119 1.9580240090 53.2797913082 -120 1.9580240090 53.2797913082 -121 1.9580240090 53.2797913082 -122 1.9909510815 54.1757698794 -123 1.9967810945 54.3344103626 -124 2.3495377688 63.9332722255 -125 2.3495377688 63.9332722255 -126 2.3495377688 63.9332722255 -127 2.4912180490 67.7885343310 -128 20.1081729795 547.1634949464 -129 20.1081729795 547.1634949464 -130 20.1081729795 547.1634949464 -131 20.1304669012 547.7701348498 -132 20.1304669012 547.7701348498 -133 20.1304669012 547.7701348498 -134 20.1813433999 549.1545352538 -135 20.1964961770 549.5668574711 -136 20.6192195219 561.0695824114 -137 20.6192195219 561.0695824114 -138 20.6192195219 561.0695824114 -139 20.6891875564 562.9734825971 -140 20.6969385212 563.1843940993 -141 20.6969385212 563.1843940993 -142 20.6969385212 563.1843940993 -143 20.7605069175 564.9141537329 -144 20.9085871992 568.9435662784 -145 20.9085871992 568.9435662784 -146 20.9085871992 568.9435662784 -147 20.9424014458 569.8636857426 -148 21.1522912000 575.5749958436 -149 21.1522912000 575.5749958436 -150 21.1522912000 575.5749958436 -151 21.2057111961 577.0286073580 -152 21.2280501556 577.6364727843 -153 21.2280501556 577.6364727843 -154 21.2280501556 577.6364727843 -155 21.2302607735 577.6966259084 -156 21.4385839521 583.3653079218 -157 21.4385839521 583.3653079218 -158 21.4385839521 583.3653079218 -159 21.5210414842 585.6090598276 -160 42.7621525954 1163.6009342744 -161 42.7621525954 1163.6009342744 -162 42.7621525954 1163.6009342744 -163 42.7980840912 1164.5786662060 -164 42.8860510290 1166.9723345503 -165 42.8860510290 1166.9723345503 -166 42.8860510290 1166.9723345503 -167 42.9401448873 1168.4442825278 -168 43.1142285714 1173.1812736557 -169 43.1142285714 1173.1812736557 -170 43.1142285714 1173.1812736557 -171 43.1360187270 1173.7742055813 -172 43.5517652522 1185.0870842781 -173 43.5517652522 1185.0870842781 -174 43.5517652522 1185.0870842781 -175 43.6850527055 1188.7139691694 -176 59.3835794777 1615.8865811678 -177 59.3835794777 1615.8865811678 -178 59.3835794777 1615.8865811678 -179 61.4891345044 1673.1808389998 diff --git a/Project#12/output/h2o/DZP/output_cis.txt b/Project#12/output/h2o/DZP/output_cis.txt deleted file mode 100644 index 44f19b4..0000000 --- a/Project#12/output/h2o/DZP/output_cis.txt +++ /dev/null @@ -1,423 +0,0 @@ -CIS Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 0.2601682546 7.0794383768 - 1 0.2601682546 7.0794383768 - 2 0.2601682546 7.0794383768 - 3 0.3020421301 8.2188684011 - 4 0.3092671403 8.4154681536 - 5 0.3092671403 8.4154681536 - 6 0.3092671403 8.4154681536 - 7 0.3238098671 8.8111902928 - 8 0.3238098671 8.8111902928 - 9 0.3238098671 8.8111902928 -10 0.3472643886 9.4494112790 -11 0.3472643886 9.4494112790 -12 0.3472643886 9.4494112790 -13 0.3531481926 9.6095154696 -14 0.4001562179 10.8886508445 -15 0.4237213482 11.5298816071 -16 0.4237213482 11.5298816071 -17 0.4237213482 11.5298816071 -18 0.4502194890 12.2509225161 -19 0.4545911157 12.3698788495 -20 0.4545911157 12.3698788495 -21 0.4545911157 12.3698788495 -22 0.4902193685 13.3393592376 -23 0.6057751931 16.4837487787 -24 0.7571664384 20.6032559549 -25 0.7571664384 20.6032559549 -26 0.7571664384 20.6032559549 -27 0.8253206540 22.4578003149 -28 0.8253206540 22.4578003149 -29 0.8253206540 22.4578003149 -30 0.8628563400 23.4791838684 -31 0.8660950514 23.5673124435 -32 0.8660950514 23.5673124435 -33 0.8660950514 23.5673124435 -34 0.9067558409 24.6737331874 -35 0.9163726675 24.9354166564 -36 0.9163726675 24.9354166564 -37 0.9163726675 24.9354166564 -38 0.9423254659 25.6416182522 -39 0.9491373141 25.8269754544 -40 0.9491373141 25.8269754544 -41 0.9491373141 25.8269754544 -42 0.9734393250 26.4882574721 -43 1.0118249726 27.5327693306 -44 1.0118249726 27.5327693306 -45 1.0118249726 27.5327693306 -46 1.0158146112 27.6413313844 -47 1.0158146112 27.6413313844 -48 1.0158146112 27.6413313844 -49 1.0253494006 27.9007825395 -50 1.0253494006 27.9007825395 -51 1.0253494006 27.9007825395 -52 1.0315669290 28.0699677050 -53 1.0315669290 28.0699677050 -54 1.0315669290 28.0699677050 -55 1.0468440310 28.4856729264 -56 1.0533283989 28.6621190622 -57 1.0609601652 28.8697870544 -58 1.0673065042 29.0424772856 -59 1.0764323878 29.2908017057 -60 1.0764323878 29.2908017057 -61 1.0764323878 29.2908017057 -62 1.0807136811 29.4072999763 -63 1.0807136811 29.4072999763 -64 1.0807136811 29.4072999763 -65 1.0827734942 29.4633495517 -66 1.0827734942 29.4633495517 -67 1.0827734942 29.4633495517 -68 1.1132271812 30.2920248279 -69 1.1178298749 30.4172687251 -70 1.1178298749 30.4172687251 -71 1.1178298749 30.4172687251 -72 1.1189626395 30.4480923825 -73 1.1189626395 30.4480923825 -74 1.1189626395 30.4480923825 -75 1.1286449377 30.7115573988 -76 1.1320244193 30.8035164748 -77 1.1320244193 30.8035164748 -78 1.1320244193 30.8035164748 -79 1.1332583987 30.8370942872 -80 1.1712502815 31.8708914092 -81 1.1751422331 31.9767953052 -82 1.1751422331 31.9767953052 -83 1.1751422331 31.9767953052 -84 1.1803594894 32.1187620649 -85 1.2121315981 32.9833129147 -86 1.2121315981 32.9833129147 -87 1.2121315981 32.9833129147 -88 1.2200137638 33.1977945259 -89 1.2295969288 33.4585620300 -90 1.2295969288 33.4585620300 -91 1.2295969288 33.4585620300 -92 1.2407339402 33.7616112464 -93 1.2545966370 34.1388290905 -94 1.2545966370 34.1388290905 -95 1.2545966370 34.1388290905 -96 1.2785815703 34.7914831102 -97 1.2962111097 35.2712005074 -98 1.3164265111 35.8212817935 -99 1.3468944465 36.6503447850 -100 1.3468944465 36.6503447850 -101 1.3468944465 36.6503447850 -102 1.4035100236 38.1909112514 -103 1.4608767640 39.7519176266 -104 1.4608767640 39.7519176266 -105 1.4608767640 39.7519176266 -106 1.5010170130 40.8441739400 -107 1.5168379085 41.2746763294 -108 1.5168379085 41.2746763294 -109 1.5168379085 41.2746763294 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-789 22.1163310587 601.8074844394 -790 22.1163310587 601.8074844394 -791 22.1267302077 602.0904556816 -792 22.2054528162 604.2325765807 -793 22.2054528162 604.2325765807 -794 22.2054528162 604.2325765807 -795 22.2169412678 604.5451888390 -796 22.4375114705 610.5471246230 -797 22.4375114705 610.5471246230 -798 22.4375114705 610.5471246230 -799 22.4382502152 610.5672266053 -800 22.4572869668 611.0852356545 -801 22.4572869668 611.0852356545 -802 22.4572869668 611.0852356545 -803 22.4581436129 611.1085458510 -804 22.6627421751 616.6758773268 -805 22.6627421751 616.6758773268 -806 22.6627421751 616.6758773268 -807 22.6639813902 616.7095976082 -808 22.9141611571 623.5172392466 -809 22.9141611571 623.5172392466 -810 22.9141611571 623.5172392466 -811 22.9313299134 623.9844182730 -812 23.1215897714 629.1615792700 -813 23.1215897714 629.1615792700 -814 23.1215897714 629.1615792700 -815 23.1368967360 629.5780970821 -816 23.6095577089 642.4396748156 -817 23.6095577089 642.4396748156 -818 23.6095577089 642.4396748156 -819 23.8432891593 648.7997413125 -820 44.7771426159 1218.4308277216 -821 44.7771426159 1218.4308277216 -822 44.7771426159 1218.4308277216 -823 44.8089454816 1219.2962155003 -824 44.9078495791 1221.9874948960 -825 44.9078495791 1221.9874948960 -826 44.9078495791 1221.9874948961 -827 44.9537204970 1223.2356884434 -828 45.1158712438 1227.6479724156 -829 45.1158712438 1227.6479724156 -830 45.1158712438 1227.6479724156 -831 45.1351492485 1228.1725461998 -832 45.5549141549 1239.5947690680 -833 45.5549141549 1239.5947690680 -834 45.5549141549 1239.5947690680 -835 45.6745123915 1242.8491566847 -836 61.5010549224 1673.5052054925 -837 61.5010549224 1673.5052054925 -838 61.5010549224 1673.5052054925 -839 63.4733960911 1727.1745810345 diff --git a/Project#12/output/h2o/DZP/output_rpa2.txt b/Project#12/output/h2o/DZP/output_rpa2.txt deleted file mode 100644 index 8ec358a..0000000 --- a/Project#12/output/h2o/DZP/output_rpa2.txt +++ /dev/null @@ -1,423 +0,0 @@ -RPA Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 0.2524202468 6.8686073354 - 1 0.2524202468 6.8686073354 - 2 0.2524202468 6.8686073354 - 3 0.2789946638 7.5917237977 - 4 0.2789946638 7.5917237977 - 5 0.2789946638 7.5917237977 - 6 0.2979651566 8.1079298774 - 7 0.3154671422 8.5841764060 - 8 0.3154671422 8.5841764060 - 9 0.3154671422 8.5841764060 -10 0.3177840684 8.6472222854 -11 0.3177840684 8.6472222854 -12 0.3177840684 8.6472222854 -13 0.3491123282 9.4996955632 -14 0.3958959851 10.7727256502 -15 0.4172439423 11.3536249129 -16 0.4172439423 11.3536249129 -17 0.4172439423 11.3536249129 -18 0.4355417100 11.8515254712 -19 0.4355417100 11.8515254712 -20 0.4355417100 11.8515254712 -21 0.4444559906 12.0940919590 -22 0.4857007528 13.2164031849 -23 0.5933921846 16.1467947358 -24 0.7388359728 20.1044656562 -25 0.7388359728 20.1044656562 -26 0.7388359728 20.1044656562 -27 0.8175786159 22.2471317161 -28 0.8175786159 22.2471317161 -29 0.8175786159 22.2471317161 -30 0.8560396031 23.2936936406 -31 0.8560396031 23.2936936406 -32 0.8560396031 23.2936936406 -33 0.8600842098 23.4037514320 -34 0.9029756199 24.5708695943 -35 0.9095587668 24.7500036021 -36 0.9095587668 24.7500036021 -37 0.9095587668 24.7500036021 -38 0.9374834224 25.5098614066 -39 0.9460299376 25.7424206333 -40 0.9460299376 25.7424206333 -41 0.9460299376 25.7424206333 -42 0.9721425699 26.4529714691 -43 1.0085650985 27.4440648959 -44 1.0085650985 27.4440648959 -45 1.0085650985 27.4440648959 -46 1.0090826643 27.4581483791 -47 1.0090826643 27.4581483791 -48 1.0090826643 27.4581483791 -49 1.0181885529 27.7059287128 -50 1.0181885529 27.7059287128 -51 1.0181885529 27.7059287128 -52 1.0233114357 27.8453274782 -53 1.0233114357 27.8453274782 -54 1.0233114357 27.8453274782 -55 1.0444932857 28.4217067983 -56 1.0485776807 28.5328472705 -57 1.0579163537 28.7869619009 -58 1.0584881485 28.8025210095 -59 1.0688720332 29.0850768945 -60 1.0688720332 29.0850768945 -61 1.0688720332 29.0850768945 -62 1.0772125337 29.3120302538 -63 1.0772125337 29.3120302538 -64 1.0772125337 29.3120302538 -65 1.0782669588 29.3407222153 -66 1.0782669588 29.3407222153 -67 1.0782669588 29.3407222153 -68 1.1117364727 30.2514611593 -69 1.1138916483 30.3101056429 -70 1.1138916483 30.3101056429 -71 1.1138916483 30.3101056429 -72 1.1176770756 30.4131109038 -73 1.1176770756 30.4131109038 -74 1.1176770756 30.4131109038 -75 1.1258723428 30.6361123197 -76 1.1279841021 30.6935754019 -77 1.1286442665 30.7115391369 -78 1.1286442665 30.7115391369 -79 1.1286442665 30.7115391369 -80 1.1677014504 31.7743241655 -81 1.1722668555 31.8985534058 -82 1.1722668555 31.8985534058 -83 1.1722668555 31.8985534058 -84 1.1790544244 32.0832499432 -85 1.2096720439 32.9163859870 -86 1.2096720439 32.9163859870 -87 1.2096720439 32.9163859870 -88 1.2181063157 33.1458909563 -89 1.2267592107 33.3813448818 -90 1.2267592107 33.3813448818 -91 1.2267592107 33.3813448818 -92 1.2395187286 33.7285441247 -93 1.2521301677 34.0717139924 -94 1.2521301677 34.0717139924 -95 1.2521301677 34.0717139924 -96 1.2662290749 34.4553593571 -97 1.2899972027 35.1021138833 -98 1.3134890648 35.7413509415 -99 1.3443317560 36.5806114137 -100 1.3443317560 36.5806114137 -101 1.3443317560 36.5806114137 -102 1.4014456539 38.1347376886 -103 1.4147514027 38.4968004185 -104 1.4587621404 39.6943766035 -105 1.4587621404 39.6943766035 -106 1.4587621404 39.6943766035 -107 1.5148142349 41.2196101457 -108 1.5148142349 41.2196101457 -109 1.5148142349 41.2196101457 -110 1.5175955501 41.2952925136 -111 1.5175955501 41.2952925136 -112 1.5175955501 41.2952925136 -113 1.5413988426 41.9430039060 -114 1.5413988426 41.9430039060 -115 1.5413988426 41.9430039060 -116 1.5575918771 42.3836325686 -117 1.5599698198 42.4483387673 -118 1.5684582747 42.6793181122 -119 1.5694892548 42.7073721110 -120 1.5694892548 42.7073721110 -121 1.5694892548 42.7073721110 -122 1.6151658223 43.9502771905 -123 1.6151658223 43.9502771905 -124 1.6151658223 43.9502771905 -125 1.6161622876 43.9773920077 -126 1.6161622876 43.9773920077 -127 1.6161622876 43.9773920077 -128 1.6286517716 44.3172433579 -129 1.6286517716 44.3172433579 -130 1.6286517716 44.3172433579 -131 1.6311975003 44.3865151805 -132 1.6311975003 44.3865151805 -133 1.6311975003 44.3865151805 -134 1.6376664405 44.5625415124 -135 1.6523246855 44.9614070166 -136 1.6693475438 45.4246160157 -137 1.6974691660 46.1898334769 -138 1.7042140714 46.3733690975 -139 1.7042140714 46.3733690975 -140 1.7042140714 46.3733690975 -141 1.7142977277 46.6477554680 -142 1.7501834429 47.6242416659 -143 1.7501834429 47.6242416659 -144 1.7501834429 47.6242416659 -145 1.7623541344 47.9554183519 -146 1.7637727806 47.9940211330 -147 1.7637727806 47.9940211330 -148 1.7637727806 47.9940211330 -149 1.7888345815 48.6759777962 -150 1.7918178165 48.7571546041 -151 1.8171888722 49.4475264007 -152 1.8265974418 49.7035429897 -153 1.8265974418 49.7035429897 -154 1.8265974418 49.7035429897 -155 1.8763858279 51.0583347641 -156 1.8763858279 51.0583347641 -157 1.8763858279 51.0583347641 -158 1.8978315491 51.6418942813 -159 1.9100417654 51.9741464790 -160 1.9100417654 51.9741464790 -161 1.9100417654 51.9741464790 -162 1.9147839567 52.1031862469 -163 1.9229233179 52.3246664043 -164 1.9316060163 52.5609313108 -165 1.9316060163 52.5609313108 -166 1.9316060163 52.5609313108 -167 1.9495069580 53.0480338329 -168 1.9495069580 53.0480338329 -169 1.9495069580 53.0480338329 -170 1.9816308561 53.9221572254 -171 2.0209811086 54.9929169455 -172 2.0209811086 54.9929169455 -173 2.0209811086 54.9929169455 -174 2.0343690961 55.3572174741 -175 2.0768197705 56.5123427743 -176 2.1168668612 57.6020641601 -177 2.1168668612 57.6020641601 -178 2.1168668612 57.6020641601 -179 2.1885715234 59.5532197226 -180 2.1885715234 59.5532197226 -181 2.1885715234 59.5532197226 -182 2.2140041174 60.2452660389 -183 2.2140041174 60.2452660389 -184 2.2140041174 60.2452660389 -185 2.2140519541 60.2465677239 -186 2.2140519541 60.2465677239 -187 2.2140519541 60.2465677239 -188 2.2279713210 60.6253276154 -189 2.2391448332 60.9293700553 -190 2.2391448332 60.9293700553 -191 2.2391448332 60.9293700553 -192 2.2409649975 60.9788985467 -193 2.2587326251 61.4623734615 -194 2.2872236090 62.2376416244 -195 2.2913484380 62.3498823463 -196 2.2913484380 62.3498823463 -197 2.2913484380 62.3498823463 -198 2.3216179089 63.1735449190 -199 2.3216179089 63.1735449190 -200 2.3216179089 63.1735449190 -201 2.3285215714 63.3614004789 -202 2.3423603290 63.7379669120 -203 2.3423603290 63.7379669120 -204 2.3423603290 63.7379669120 -205 2.3466336891 63.8542493153 -206 2.3501019808 63.9486249988 -207 2.3756542314 64.6439272914 -208 2.3756542314 64.6439272914 -209 2.3756542314 64.6439272914 -210 2.4149110853 65.7121455428 -211 2.4308266124 66.1452229487 -212 2.4308266124 66.1452229487 -213 2.4308266124 66.1452229487 -214 2.4472217136 66.5913500500 -215 2.4592161862 66.9177316418 -216 2.4592161862 66.9177316418 -217 2.4592161862 66.9177316418 -218 2.5218505325 68.6220748385 -219 2.5218505325 68.6220748385 -220 2.5218505325 68.6220748385 -221 2.5506768645 69.4064681606 -222 2.5632281690 69.7480017056 -223 2.5632281690 69.7480017056 -224 2.5632281690 69.7480017056 -225 2.5908891238 70.5006839470 -226 2.6028948703 70.8273723155 -227 2.6092597085 71.0005659291 -228 2.6514557669 72.1487628740 -229 2.6514557669 72.1487628740 -230 2.6514557669 72.1487628740 -231 2.6526599848 72.1815308477 -232 2.6526599848 72.1815308477 -233 2.6526599848 72.1815308477 -234 2.6582365342 72.3332743322 -235 2.6582365342 72.3332743322 -236 2.6582365342 72.3332743322 -237 2.6676917341 72.5905597760 -238 2.6783913012 72.8817056964 -239 2.7044401807 73.5905217566 -240 2.7044401807 73.5905217566 -241 2.7044401807 73.5905217566 -242 2.7163688390 73.9151124777 -243 2.7333735989 74.3778290002 -244 2.7333735989 74.3778290002 -245 2.7333735989 74.3778290002 -246 2.7643529113 75.2208070695 -247 2.8593393996 77.8054844019 -248 2.8593393996 77.8054844019 -249 2.8593393996 77.8054844019 -250 2.8628330821 77.9005509972 -251 2.8878582573 78.5815110399 -252 2.8878582573 78.5815110399 -253 2.8878582573 78.5815110399 -254 2.9206409115 79.4735598438 -255 2.9545130093 80.3952534950 -256 2.9545130093 80.3952534950 -257 2.9545130093 80.3952534950 -258 2.9584517538 80.5024306740 -259 2.9584517538 80.5024306740 -260 2.9584517538 80.5024306740 -261 2.9717874147 80.8653073407 -262 3.0278919141 82.3919668746 -263 3.0431365421 82.8067884470 -264 3.0445930497 82.8464214745 -265 3.0445930497 82.8464214745 -266 3.0445930497 82.8464214745 -267 3.0873483797 84.0098367594 -268 3.1269637141 85.0878096245 -269 3.1269637141 85.0878096245 -270 3.1269637141 85.0878096245 -271 3.1906181253 86.8199098082 -272 3.2119244687 87.3996767191 -273 3.2119244687 87.3996767191 -274 3.2119244687 87.3996767191 -275 3.2182518260 87.5718504377 -276 3.2182518260 87.5718504377 -277 3.2182518260 87.5718504377 -278 3.2360488416 88.0561250295 -279 3.2548778703 88.5684817293 -280 3.2548778703 88.5684817293 -281 3.2548778703 88.5684817293 -282 3.2673859793 88.9088398819 -283 3.2673859793 88.9088398819 -284 3.2673859793 88.9088398819 -285 3.2943054919 89.6413467411 -286 3.3308620350 90.6360868351 -287 3.3509247309 91.1820128526 -288 3.3690220260 91.6744583495 -289 3.3690220260 91.6744583495 -290 3.3690220260 91.6744583495 -291 3.4473409443 93.8055944345 -292 3.4473409443 93.8055944345 -293 3.4473409443 93.8055944345 -294 3.4617597933 94.1979457367 -295 3.5233426696 95.8736773814 -296 3.7286344717 101.4598726089 -297 3.7286344717 101.4598726089 -298 3.7286344717 101.4598726089 -299 3.7908636297 103.1531902282 -300 3.9647664393 107.8852595792 -301 3.9647664393 107.8852595792 -302 3.9647664393 107.8852595792 -303 3.9987364043 108.8096162964 -304 3.9987364043 108.8096162964 -305 3.9987364043 108.8096162964 -306 4.0394064172 109.9162880183 -307 4.0664304733 110.6516396103 -308 4.0854069259 111.1680078593 -309 4.0854069259 111.1680078593 -310 4.0854069259 111.1680078593 -311 4.1697446510 113.4629216975 -312 4.2369405581 115.2913895257 -313 4.2369405581 115.2913895257 -314 4.2369405581 115.2913895257 -315 4.2787072347 116.4279025639 -316 4.7930213471 130.4229038772 -317 4.7930213471 130.4229038772 -318 4.7930213471 130.4229038772 -319 4.9116249052 133.6502252947 -320 20.1255866300 547.6373377891 -321 20.1255866300 547.6373377891 -322 20.1255866300 547.6373377891 -323 20.1452865691 548.1733928331 -324 20.1452865691 548.1733928331 -325 20.1452865691 548.1733928331 -326 20.1992379048 549.6414626277 -327 20.2110785961 549.9636596786 -328 20.6145455376 560.9423986245 -329 20.6145455376 560.9423986245 -330 20.6145455376 560.9423986245 -331 20.6758791969 562.6113488259 -332 20.6758791969 562.6113488259 -333 20.6758791969 562.6113488259 -334 20.6850341383 562.8604639370 -335 20.7374556000 564.2869043322 -336 20.8877828887 568.3774601831 -337 20.8877828887 568.3774601831 -338 20.8877828887 568.3774601831 -339 20.9167537301 569.1657857487 -340 21.0745234675 573.4588580731 -341 21.0745234675 573.4588580731 -342 21.0745234675 573.4588580731 -343 21.1155916516 574.5763644326 -344 21.1414995441 575.2813440956 -345 21.1414995441 575.2813440956 -346 21.1414995441 575.2813440956 -347 21.1452066276 575.3822175433 -348 21.1944833788 576.7230872192 -349 21.1944833788 576.7230872192 -350 21.1944833788 576.7230872192 -351 21.2132424551 577.2335404465 -352 21.5016078980 585.0802525132 -353 21.5016078980 585.0802525132 -354 21.5016078980 585.0802525132 -355 21.5018738622 585.0874896632 -356 21.5474330860 586.3272017020 -357 21.5474330860 586.3272017020 -358 21.5474330860 586.3272017020 -359 21.5490603944 586.3714823922 -360 21.6536064976 589.2162864054 -361 21.6536064976 589.2162864054 -362 21.6536064976 589.2162864054 -363 21.6539678176 589.2261182848 -364 21.9657646993 597.7104232334 -365 21.9657646993 597.7104232334 -366 21.9657646993 597.7104232334 -367 21.9657769931 597.7107577599 -368 22.1163310587 601.8074844394 -369 22.1163310587 601.8074844394 -370 22.1163310587 601.8074844394 -371 22.1267302077 602.0904556816 -372 22.2054528162 604.2325765807 -373 22.2054528162 604.2325765807 -374 22.2054528162 604.2325765807 -375 22.2169412678 604.5451888390 -376 22.4375114705 610.5471246230 -377 22.4375114705 610.5471246230 -378 22.4375114705 610.5471246230 -379 22.4382502152 610.5672266053 -380 22.4572869668 611.0852356545 -381 22.4572869668 611.0852356545 -382 22.4572869668 611.0852356545 -383 22.4581436129 611.1085458510 -384 22.6627421751 616.6758773268 -385 22.6627421751 616.6758773268 -386 22.6627421751 616.6758773268 -387 22.6639813902 616.7095976082 -388 22.9141611571 623.5172392466 -389 22.9141611571 623.5172392466 -390 22.9141611571 623.5172392466 -391 22.9313299134 623.9844182730 -392 23.1215897714 629.1615792700 -393 23.1215897714 629.1615792700 -394 23.1215897714 629.1615792700 -395 23.1368967360 629.5780970821 -396 23.6095577089 642.4396748156 -397 23.6095577089 642.4396748156 -398 23.6095577089 642.4396748156 -399 23.8432891593 648.7997413125 -400 44.7771426159 1218.4308277216 -401 44.7771426159 1218.4308277216 -402 44.7771426159 1218.4308277216 -403 44.8089454816 1219.2962155003 -404 44.9078495791 1221.9874948960 -405 44.9078495791 1221.9874948960 -406 44.9078495791 1221.9874948960 -407 44.9537204970 1223.2356884434 -408 45.1158712438 1227.6479724155 -409 45.1158712438 1227.6479724155 -410 45.1158712438 1227.6479724155 -411 45.1351492485 1228.1725461998 -412 45.5549141549 1239.5947690680 -413 45.5549141549 1239.5947690680 -414 45.5549141549 1239.5947690680 -415 45.6745123915 1242.8491566847 -416 61.5010549224 1673.5052054925 -417 61.5010549224 1673.5052054925 -418 61.5010549224 1673.5052054925 -419 63.4733960911 1727.1745810345 diff --git a/Project#12/output/h2o/STO-3G/output_cis.txt b/Project#12/output/h2o/STO-3G/output_cis.txt deleted file mode 100644 index c4a8b36..0000000 --- a/Project#12/output/h2o/STO-3G/output_cis.txt +++ /dev/null @@ -1,43 +0,0 @@ -CIS Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 0.2872554996 7.8165094000 - 1 0.2872554996 7.8165094000 - 2 0.2872554996 7.8165094000 - 3 0.3444249963 9.3721485742 - 4 0.3444249963 9.3721485742 - 5 0.3444249963 9.3721485742 - 6 0.3564617587 9.6996809147 - 7 0.3659889948 9.9589265386 - 8 0.3659889948 9.9589265386 - 9 0.3659889948 9.9589265386 -10 0.3945137992 10.7351149906 -11 0.3945137992 10.7351149906 -12 0.3945137992 10.7351149906 -13 0.4160717386 11.3217280788 -14 0.5056282877 13.7586513356 -15 0.5142899971 13.9943451123 -16 0.5142899971 13.9943451123 -17 0.5142899971 13.9943451123 -18 0.5551918860 15.1073264088 -19 0.5630557635 15.3213103815 -20 0.5630557635 15.3213103815 -21 0.5630557635 15.3213103815 -22 0.6553184485 17.8318703012 -23 0.9101216891 24.7653212808 -24 1.1087709658 30.1707667495 -25 1.1087709658 30.1707667495 -26 1.1087709658 30.1707667495 -27 1.2000961331 32.6558158774 -28 1.2000961331 32.6558158774 -29 1.2000961331 32.6558158774 -30 1.3007851948 35.3956659366 -31 1.3257620652 36.0753115562 -32 19.9585264123 543.0914622058 -33 19.9585264123 543.0914622058 -34 19.9585264123 543.0914622058 -35 20.0109794203 544.5187610062 -36 20.0113420895 544.5286295981 -37 20.0113420895 544.5286295981 -38 20.0113420895 544.5286295981 -39 20.0505319444 545.5950247379 diff --git a/Project#12/output/h2o/STO-3G/output_rpa1.txt b/Project#12/output/h2o/STO-3G/output_rpa1.txt deleted file mode 100644 index 321fd22..0000000 --- a/Project#12/output/h2o/STO-3G/output_rpa1.txt +++ /dev/null @@ -1,83 +0,0 @@ -RPA Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 -20.0504919449 -545.5939363129 - 1 -20.0113074586 -544.5276872551 - 2 -20.0113074586 -544.5276872551 - 3 -20.0113074586 -544.5276872551 - 4 -20.0109471551 -544.5178830377 - 5 -19.9585040647 -543.0908541050 - 6 -19.9585040647 -543.0908541050 - 7 -19.9585040647 -543.0908541050 - 8 -1.3237421886 -36.0203486946 - 9 -1.2832053178 -34.9172999015 -10 -1.1957870714 -32.5385620002 -11 -1.1957870714 -32.5385620002 -12 -1.1957870714 -32.5385620002 -13 -1.1038187957 -30.0360132492 -14 -1.1038187957 -30.0360132492 -15 -1.1038187957 -30.0360132492 -16 -0.8734253708 -23.7667777637 -17 -0.6502707118 -17.6945163383 -18 -0.5513718846 -15.0033803508 -19 -0.5460719086 -14.8591627038 -20 -0.5460719086 -14.8591627038 -21 -0.5460719086 -14.8591627038 -22 -0.5106610509 -13.8955978550 -23 -0.5106610509 -13.8955978550 -24 -0.5106610509 -13.8955978550 -25 -0.5001011401 -13.6082521222 -26 -0.4153174946 -11.3012043465 -27 -0.3651313107 -9.9355880949 -28 -0.3651313107 -9.9355880949 -29 -0.3651313107 -9.9355880949 -30 -0.3547782530 -9.6538710427 -31 -0.3526266606 -9.5953240628 -32 -0.3526266606 -9.5953240628 -33 -0.3526266606 -9.5953240628 -34 -0.2997434467 -8.1563189292 -35 -0.2997434467 -8.1563189292 -36 -0.2997434467 -8.1563189292 -37 -0.2851637170 -7.7595899029 -38 -0.2851637170 -7.7595899029 -39 -0.2851637170 -7.7595899029 -40 0.2851637170 7.7595899029 -41 0.2851637170 7.7595899029 -42 0.2851637170 7.7595899029 -43 0.2997434467 8.1563189292 -44 0.2997434467 8.1563189292 -45 0.2997434467 8.1563189292 -46 0.3526266606 9.5953240628 -47 0.3526266606 9.5953240628 -48 0.3526266606 9.5953240628 -49 0.3547782530 9.6538710427 -50 0.3651313107 9.9355880949 -51 0.3651313107 9.9355880949 -52 0.3651313107 9.9355880949 -53 0.4153174946 11.3012043465 -54 0.5001011401 13.6082521222 -55 0.5106610509 13.8955978550 -56 0.5106610509 13.8955978550 -57 0.5106610509 13.8955978550 -58 0.5460719086 14.8591627038 -59 0.5460719086 14.8591627038 -60 0.5460719086 14.8591627038 -61 0.5513718846 15.0033803508 -62 0.6502707118 17.6945163383 -63 0.8734253708 23.7667777637 -64 1.1038187957 30.0360132492 -65 1.1038187957 30.0360132492 -66 1.1038187957 30.0360132492 -67 1.1957870714 32.5385620002 -68 1.1957870714 32.5385620002 -69 1.1957870714 32.5385620002 -70 1.2832053178 34.9172999015 -71 1.3237421886 36.0203486946 -72 19.9585040647 543.0908541050 -73 19.9585040647 543.0908541050 -74 19.9585040647 543.0908541050 -75 20.0109471551 544.5178830377 -76 20.0113074586 544.5276872551 -77 20.0113074586 544.5276872551 -78 20.0113074586 544.5276872551 -79 20.0504919449 545.5939363129 diff --git a/Project#12/output/h2o/STO-3G/output_rpa2.txt b/Project#12/output/h2o/STO-3G/output_rpa2.txt deleted file mode 100644 index 8385a9c..0000000 --- a/Project#12/output/h2o/STO-3G/output_rpa2.txt +++ /dev/null @@ -1,43 +0,0 @@ -RPA Excitation Energies: - # Hartree eV --- -------------------- -------------------- - 0 0.2851637170 7.7595899029 - 1 0.2851637170 7.7595899029 - 2 0.2851637170 7.7595899029 - 3 0.2997434467 8.1563189292 - 4 0.2997434467 8.1563189292 - 5 0.2997434467 8.1563189292 - 6 0.3526266606 9.5953240628 - 7 0.3526266606 9.5953240628 - 8 0.3526266606 9.5953240628 - 9 0.3547782530 9.6538710427 -10 0.3651313107 9.9355880949 -11 0.3651313107 9.9355880949 -12 0.3651313107 9.9355880949 -13 0.4153174946 11.3012043465 -14 0.5001011401 13.6082521222 -15 0.5106610509 13.8955978550 -16 0.5106610509 13.8955978550 -17 0.5106610509 13.8955978550 -18 0.5460719086 14.8591627038 -19 0.5460719086 14.8591627038 -20 0.5460719086 14.8591627038 -21 0.5513718846 15.0033803508 -22 0.6502707118 17.6945163383 -23 0.8734253708 23.7667777637 -24 1.1038187957 30.0360132492 -25 1.1038187957 30.0360132492 -26 1.1038187957 30.0360132492 -27 1.1957870714 32.5385620002 -28 1.1957870714 32.5385620002 -29 1.1957870714 32.5385620002 -30 1.2832053178 34.9172999015 -31 1.3237421886 36.0203486946 -32 19.9585040647 543.0908541050 -33 19.9585040647 543.0908541050 -34 19.9585040647 543.0908541050 -35 20.0109471551 544.5178830377 -36 20.0113074586 544.5276872551 -37 20.0113074586 544.5276872551 -38 20.0113074586 544.5276872551 -39 20.0504919449 545.5939363129 diff --git a/Project#13/README.md b/Project#13/README.md deleted file mode 100644 index 54d22da..0000000 --- a/Project#13/README.md +++ /dev/null @@ -1,113 +0,0 @@ -# Project #13: The Davidson-Liu Algorithm: CIS - -A common problem in quantum chemistry is the need to compute a few eigenvalues -of a very large matrix -- far too large to store entirely in core memory. In -1975, Ernest Davidson published a robust algorithm[1](#f1) -to solve this problem, and it has been used in electronic structure -software packages ever since. A few years later, Bowen Liu extended the -algorithm to allow computation of several eigenvalues simultaneously rather -than one at a time[2](#f2). The -purpose of this project is to illustrate the use of what is now called the -Davidson-Liu algorithm in the context of a -[CIS computation](../Project%2312). - -## The Basic Algorithm - -This is an outline of the essential aspects of the Davidson-Liu algorithm. -There are many ways to tweak the approach to improve its rate of convergence or -efficiency, and for details I recommend David Sherrill's excellent CI review -article[3](#f3), from which also we take our notation below. - -## Step #1: Select Guess Vectors - -Compute a set of *L* orthonormal guess eigenvectors, {***b***i} --- -at least one for every desired root. A simple choice is a set of unit vectors, -or one can taken them from another level of theory or perhaps the eigenvectors -from a well-chosen subspace of the full determinantal space. - -## Step #2: Build and Diagonalize the Subspace Hamiltonian - -Compute a representation of the Hamiltonian within the space of guess vectors, - - - -and then diagonalize this so-called "subspace Hamiltonian", - - - -where *M* is the number of roots of interest. The current estimate of each of -the *M* eigenvectors we want is a linear combination of the guess vectors, -with the αk subspace eigenvectors providing the -coefficients, *viz.* - - - -The dimension of ***G*** is typically very small (perhaps a dozen times the -number of guess vectors, *L*), so one can used a standard diagonalization -package (such as DSYEV in LAPACK) for this task. Note that the most expensive -part of the Davidson-Liu algorithm is the computation of σ, -the products of the Hamiltonian matrix with the guess vectors. In some of the -largest CI calculations, the Hamiltonian cannot even be stored on disk and its -elements must be computed "on the fly" during the computation of each -σ. - -## Step #3: Build the Correction Vectors - -Build a set of "correction vectors", - - - -where the "residual" vectors are defined as - - - -and *N* is the dimension of the Hamiltonian (i.e. the number of determinants). -The inverse appearing in the definition of the correction vectors is commonly -referred to as the "preconditioner". Notice that the residual vectors are so -named because they would be zero if the guess vectors, ***b***i, -were the true eigenvectors. Thus, convergence of the algorithm is checked at -this point, based on the norms of the residual vectors (one for each desired -root) and the change in the corresponding eigenvalue between each iteration. -## Step #4: Orthonormalize the Correction Vectors - -Normalize each correction vector, fδk, -then orthogonalize it against the existing set of guesses, **b**i, -using the [Schmidt Orthogonalization procedure](http://en.wikipedia.org/wiki/Gram–Schmidt_process), -for example. If the orthonormalized correction vector has a norm larger than some chosen threshold (e.g. 10-3), -include it in the set of guess vectors. If not, discard it. (Thus, the dimension of the guess space, *L*, gradually increases in each iteration.) - -Return to step #2 and continue. - -## CIS Sigma Equation - -We will focus on the spin-adapted singlet formulation of CIS, -for which the σ = H c equation was given in -[Project 12](../Project%2312): - - - -## Unit Guess Vectors - -What should we choose for guess vectors? As noted above, the simplest choice -is probably a set of unit vectors, one for each eigenvalue you want. But in -what position of the vector should we put the 1? For a hint, look at the -structure of the [spin-adapted singlet CIS Hamiltonian](../Project%2312/hints/hint2.md) -for the H2O STO-3G test case and note that it is -strongly diagonally dominant. Thus, if the diagonal elements are reasonable -approximations to the true eigenvalues, and we want to compute only the lowest -*M* eigenvalues, then our guess unit vectors should have a 1 in the position -corresponding to the row/column of the smallest elements of the Hamiltonian. - -## Subspace Collapse - -If the number of guess vectors grows to be too large, we may need to reduce its -dimension to something more manageable before continuing the Davidson-Liu -algorithm. A typical choice is to collapse to the current best set of guesses -using the equation given above for the current final eigenvectors: - - - -#### References - - 1: E.R. Davidson, "The iterative calculation of a few of the lowest eigenvalues and corresponding eigenvectors of large real-symmetric matrices," *J. Comput. Phys.* **17**, 87 (1975). [(return to text)](#r1) - - 2: B.Liu, "The simultaneous expansion method for the iterative solution of several of the lowest eigenvalues and corresponding eigenvectors of large real-symmetric matrices," Technical Report LBL-8158, Lawrence Berkeley Laboratory, University of California, Berkeley, 1978. [(return to text)](#r2) - - 3: C.D. Sherrill, "The Configuration Interaction Method: Advances in Highly Correlated Approaches," *Adv. Quantum Chem.* **34**, 143 (1998). 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