! --- subroutine single_htilde_mu_mat_fock_bi_ortho(Nint, key_j, key_i, hmono, htwoe, hthree, htot) BEGIN_DOC ! ! for single excitation ONLY FOR ONE- AND TWO-BODY TERMS !! !! WARNING !! ! ! Non hermitian !! ! END_DOC use bitmasks implicit none integer, intent(in) :: Nint integer(bit_kind), intent(in) :: key_j(Nint,2), key_i(Nint,2) double precision, intent(out) :: hmono, htwoe, hthree, htot integer :: occ(Nint*bit_kind_size,2) integer :: Ne(2), i, j, ii, jj, ispin, jspin, k, kk integer :: degree,exc(0:2,2,2) integer :: h1, p1, h2, p2, s1, s2 double precision :: get_mo_two_e_integral_tc_int, phase double precision :: direct_int, exchange_int_12, exchange_int_23, exchange_int_13 integer :: other_spin(2) integer(bit_kind) :: key_j_core(Nint,2), key_i_core(Nint,2) other_spin(1) = 2 other_spin(2) = 1 hmono = 0.d0 htwoe = 0.d0 hthree = 0.d0 htot = 0.d0 call get_excitation_degree(key_i, key_j, degree, Nint) if(degree .ne. 1) then return endif call bitstring_to_list_ab(key_i, occ, Ne, Nint) call get_single_excitation(key_i, key_j, exc, phase, Nint) call decode_exc(exc, 1, h1, p1, h2, p2, s1, s2) call get_single_excitation_from_fock_tc(Nint, key_i, key_j, h1, p1, s1, phase, hmono, htwoe, hthree, htot) end ! --- subroutine get_single_excitation_from_fock_tc(Nint, key_i, key_j, h, p, spin, phase, hmono, htwoe, hthree, htot) use bitmasks implicit none integer, intent(in) :: Nint integer, intent(in) :: h, p, spin double precision, intent(in) :: phase integer(bit_kind), intent(in) :: key_i(Nint,2), key_j(Nint,2) double precision, intent(out) :: hmono, htwoe, hthree, htot integer(bit_kind) :: differences(Nint,2) integer(bit_kind) :: hole(Nint,2) integer(bit_kind) :: partcl(Nint,2) integer :: occ_hole(Nint*bit_kind_size,2) integer :: occ_partcl(Nint*bit_kind_size,2) integer :: n_occ_ab_hole(2),n_occ_ab_partcl(2) integer :: i0,i double precision :: buffer_c(mo_num),buffer_x(mo_num) do i = 1, mo_num buffer_c(i) = tc_2e_3idx_coulomb_integrals (i,p,h) buffer_x(i) = tc_2e_3idx_exchange_integrals(i,p,h) enddo do i = 1, Nint differences(i,1) = xor(key_i(i,1), ref_closed_shell_bitmask(i,1)) differences(i,2) = xor(key_i(i,2), ref_closed_shell_bitmask(i,2)) hole (i,1) = iand(differences(i,1), ref_closed_shell_bitmask(i,1)) hole (i,2) = iand(differences(i,2), ref_closed_shell_bitmask(i,2)) partcl (i,1) = iand(differences(i,1), key_i(i,1)) partcl (i,2) = iand(differences(i,2), key_i(i,2)) enddo call bitstring_to_list_ab(hole, occ_hole, n_occ_ab_hole, Nint) call bitstring_to_list_ab(partcl, occ_partcl, n_occ_ab_partcl, Nint) hmono = mo_bi_ortho_tc_one_e(p,h) htwoe = fock_op_2_e_tc_closed_shell(p,h) ! holes :: direct terms do i0 = 1, n_occ_ab_hole(1) i = occ_hole(i0,1) htwoe -= buffer_c(i) enddo do i0 = 1, n_occ_ab_hole(2) i = occ_hole(i0,2) htwoe -= buffer_c(i) enddo ! holes :: exchange terms do i0 = 1, n_occ_ab_hole(spin) i = occ_hole(i0,spin) htwoe += buffer_x(i) enddo ! particles :: direct terms do i0 = 1, n_occ_ab_partcl(1) i = occ_partcl(i0,1) htwoe += buffer_c(i) enddo do i0 = 1, n_occ_ab_partcl(2) i = occ_partcl(i0,2) htwoe += buffer_c(i) enddo ! particles :: exchange terms do i0 = 1, n_occ_ab_partcl(spin) i = occ_partcl(i0,spin) htwoe -= buffer_x(i) enddo hthree = 0.d0 if (three_body_h_tc .and. elec_num.gt.2 .and. three_e_4_idx_term) then call three_comp_fock_elem(Nint, key_i, h, p, spin, hthree) endif htwoe = htwoe * phase hmono = hmono * phase hthree = hthree * phase htot = htwoe + hmono + hthree end ! --- subroutine three_comp_fock_elem(Nint, key_i, h_fock, p_fock, ispin_fock, hthree) implicit none integer, intent(in) :: Nint integer, intent(in) :: h_fock, p_fock, ispin_fock integer(bit_kind), intent(in) :: key_i(Nint,2) double precision, intent(out) :: hthree integer :: nexc(2),i,ispin,na,nb integer(bit_kind) :: hole(Nint,2) integer(bit_kind) :: particle(Nint,2) integer :: occ_hole(Nint*bit_kind_size,2) integer :: occ_particle(Nint*bit_kind_size,2) integer :: n_occ_ab_hole(2),n_occ_ab_particle(2) integer(bit_kind) :: det_tmp(Nint,2) nexc(1) = 0 nexc(2) = 0 !! Get all the holes and particles of key_i with respect to the ROHF determinant do i = 1, Nint hole(i,1) = xor(key_i(i,1),ref_bitmask(i,1)) hole(i,2) = xor(key_i(i,2),ref_bitmask(i,2)) particle(i,1) = iand(hole(i,1),key_i(i,1)) particle(i,2) = iand(hole(i,2),key_i(i,2)) hole(i,1) = iand(hole(i,1),ref_bitmask(i,1)) hole(i,2) = iand(hole(i,2),ref_bitmask(i,2)) nexc(1) = nexc(1) + popcnt(hole(i,1)) nexc(2) = nexc(2) + popcnt(hole(i,2)) enddo integer :: tmp(2) !DIR$ FORCEINLINE call bitstring_to_list_ab(particle, occ_particle, tmp, Nint) ASSERT (tmp(1) == nexc(1)) ! Number of particles alpha ASSERT (tmp(2) == nexc(2)) ! Number of particle beta !DIR$ FORCEINLINE call bitstring_to_list_ab(hole, occ_hole, tmp, Nint) ASSERT (tmp(1) == nexc(1)) ! Number of holes alpha ASSERT (tmp(2) == nexc(2)) ! Number of holes beta !! Initialize the matrix element with the reference ROHF Slater determinant Fock element if(ispin_fock==1)then hthree = fock_a_tot_3e_bi_orth(p_fock,h_fock) else hthree = fock_b_tot_3e_bi_orth(p_fock,h_fock) endif det_tmp = ref_bitmask do ispin=1,2 na = elec_num_tab(ispin) nb = elec_num_tab(iand(ispin,1)+1) do i = 1, nexc(ispin) !DIR$ FORCEINLINE call fock_ac_tc_operator( occ_particle(i,ispin), ispin, det_tmp, h_fock,p_fock, ispin_fock, hthree, Nint, na, nb) !DIR$ FORCEINLINE call fock_a_tc_operator ( occ_hole (i,ispin), ispin, det_tmp, h_fock,p_fock, ispin_fock, hthree, Nint, na, nb) enddo enddo end ! --- subroutine fock_ac_tc_operator(iorb,ispin,key, h_fock,p_fock, ispin_fock,hthree,Nint,na,nb) use bitmasks implicit none BEGIN_DOC ! Routine that computes the contribution to the three-electron part of the Fock operator ! ! a^dagger_{p_fock} a_{h_fock} of spin ispin_fock ! ! on top of a determinant 'key' on which you ADD an electron of spin ispin in orbital iorb ! ! in output, the determinant key is changed by the ADDITION of that electron ! ! the output hthree is INCREMENTED END_DOC integer, intent(in) :: iorb, ispin, Nint, h_fock,p_fock, ispin_fock integer, intent(inout) :: na, nb integer(bit_kind), intent(inout) :: key(Nint,2) double precision, intent(inout) :: hthree integer :: occ(Nint*bit_kind_size,2) integer :: other_spin integer :: k,l,i,jj,j double precision :: direct_int, exchange_int if (iorb < 1) then print *, irp_here, ': iorb < 1' print *, iorb, mo_num stop -1 endif if (iorb > mo_num) then print *, irp_here, ': iorb > mo_num' print *, iorb, mo_num stop -1 endif ASSERT (ispin > 0) ASSERT (ispin < 3) ASSERT (Nint > 0) integer :: tmp(2) !DIR$ FORCEINLINE call bitstring_to_list_ab(key, occ, tmp, Nint) ASSERT (tmp(1) == elec_alpha_num) ASSERT (tmp(2) == elec_beta_num) k = shiftr(iorb-1,bit_kind_shift)+1 ASSERT (k >0) l = iorb - shiftl(k-1,bit_kind_shift)-1 ASSERT (l >= 0) key(k,ispin) = ibset(key(k,ispin),l) other_spin = iand(ispin,1)+1 !! spin of other electrons == ispin if(ispin == ispin_fock)then !! in what follows :: jj == other electrons in the determinant !! :: iorb == electron that has been added of spin ispin !! :: p_fock, h_fock == hole particle of spin ispin_fock !! jj = ispin = ispin_fock >> pure parallel spin do j = 1, na jj = occ(j,ispin) hthree += three_e_single_parrallel_spin_prov(jj,iorb,p_fock,h_fock) enddo !! spin of jj == other spin than ispin AND ispin_fock !! exchange between the iorb and (h_fock, p_fock) do j = 1, nb jj = occ(j,other_spin) direct_int = three_e_4_idx_direct_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR ! TODO ! use transpose exchange_int = three_e_4_idx_exch13_bi_ort(iorb,jj,p_fock,h_fock) ! USES 4-IDX TENSOR hthree += direct_int - exchange_int enddo else !! ispin NE to ispin_fock !! jj = ispin BUT NON EQUAL TO ispin_fock !! exchange between the jj and iorb do j = 1, na jj = occ(j,ispin) direct_int = three_e_4_idx_direct_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR exchange_int = three_e_4_idx_exch23_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR hthree += direct_int - exchange_int enddo !! jj = other_spin than ispin BUT jj == ispin_fock !! exchange between jj and (h_fock,p_fock) do j = 1, nb jj = occ(j,other_spin) direct_int = three_e_4_idx_direct_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR exchange_int = three_e_4_idx_exch13_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR hthree += direct_int - exchange_int enddo endif na = na+1 end subroutine fock_a_tc_operator(iorb,ispin,key, h_fock,p_fock, ispin_fock,hthree,Nint,na,nb) use bitmasks implicit none BEGIN_DOC ! Routine that computes the contribution to the three-electron part of the Fock operator ! ! a^dagger_{p_fock} a_{h_fock} of spin ispin_fock ! ! on top of a determinant 'key' on which you REMOVE an electron of spin ispin in orbital iorb ! ! in output, the determinant key is changed by the REMOVAL of that electron ! ! the output hthree is INCREMENTED END_DOC integer, intent(in) :: iorb, ispin, Nint, h_fock,p_fock, ispin_fock integer, intent(inout) :: na, nb integer(bit_kind), intent(inout) :: key(Nint,2) double precision, intent(inout) :: hthree double precision :: direct_int, exchange_int integer :: occ(Nint*bit_kind_size,2) integer :: other_spin integer :: k,l,i,jj,mm,j,m integer :: tmp(2) ASSERT (iorb > 0) ASSERT (ispin > 0) ASSERT (ispin < 3) ASSERT (Nint > 0) k = shiftr(iorb-1,bit_kind_shift)+1 ASSERT (k>0) l = iorb - shiftl(k-1,bit_kind_shift)-1 key(k,ispin) = ibclr(key(k,ispin),l) other_spin = iand(ispin,1)+1 !DIR$ FORCEINLINE call bitstring_to_list_ab(key, occ, tmp, Nint) na = na-1 !! spin of other electrons == ispin if(ispin == ispin_fock)then !! in what follows :: jj == other electrons in the determinant !! :: iorb == electron that has been added of spin ispin !! :: p_fock, h_fock == hole particle of spin ispin_fock !! jj = ispin = ispin_fock >> pure parallel spin do j = 1, na jj = occ(j,ispin) hthree -= three_e_single_parrallel_spin_prov(jj,iorb,p_fock,h_fock) enddo !! spin of jj == other spin than ispin AND ispin_fock !! exchange between the iorb and (h_fock, p_fock) do j = 1, nb jj = occ(j,other_spin) direct_int = three_e_4_idx_direct_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR ! TODO use transpose exchange_int = three_e_4_idx_exch13_bi_ort(iorb,jj,p_fock,h_fock) ! USES 4-IDX TENSOR hthree -= direct_int - exchange_int enddo else !! ispin NE to ispin_fock !! jj = ispin BUT NON EQUAL TO ispin_fock !! exchange between the jj and iorb do j = 1, na jj = occ(j,ispin) direct_int = three_e_4_idx_direct_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR exchange_int = three_e_4_idx_exch23_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR hthree -= direct_int - exchange_int enddo !! jj = other_spin than ispin BUT jj == ispin_fock !! exchange between jj and (h_fock,p_fock) do j = 1, nb jj = occ(j,other_spin) direct_int = three_e_4_idx_direct_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR exchange_int = three_e_4_idx_exch13_bi_ort(jj,iorb,p_fock,h_fock) ! USES 4-IDX TENSOR hthree -= direct_int - exchange_int enddo endif end ! --- BEGIN_PROVIDER [double precision, fock_op_2_e_tc_closed_shell, (mo_num, mo_num)] BEGIN_DOC ! Closed-shell part of the Fock operator for the TC operator END_DOC implicit none PROVIDE N_int integer :: h0,p0,h,p,k0,k,i integer :: n_occ_ab(2) integer :: occ(N_int*bit_kind_size,2) integer :: n_occ_ab_virt(2) integer :: occ_virt(N_int*bit_kind_size,2) integer(bit_kind) :: key_test(N_int) integer(bit_kind) :: key_virt(N_int,2) double precision :: accu fock_op_2_e_tc_closed_shell = -1000.d0 call bitstring_to_list_ab(ref_closed_shell_bitmask, occ, n_occ_ab, N_int) do i = 1, N_int key_virt(i,1) = full_ijkl_bitmask(i) key_virt(i,2) = full_ijkl_bitmask(i) key_virt(i,1) = xor(key_virt(i,1),ref_closed_shell_bitmask(i,1)) key_virt(i,2) = xor(key_virt(i,2),ref_closed_shell_bitmask(i,2)) enddo call bitstring_to_list_ab(key_virt, occ_virt, n_occ_ab_virt, N_int) ! docc ---> virt single excitations do h0 = 1, n_occ_ab(1) h = occ(h0,1) do p0 = 1, n_occ_ab_virt(1) p = occ_virt(p0,1) accu = 0.d0 do k0 = 1, n_occ_ab(1) k = occ(k0,1) accu += 2.d0 * tc_2e_3idx_coulomb_integrals(k,p,h) - tc_2e_3idx_exchange_integrals(k,p,h) enddo fock_op_2_e_tc_closed_shell(p,h) = accu enddo enddo do h0 = 1, n_occ_ab_virt(1) h = occ_virt(h0,1) do p0 = 1, n_occ_ab(1) p = occ(p0,1) accu = 0.d0 do k0 = 1, n_occ_ab(1) k = occ(k0,1) accu += 2.d0 * tc_2e_3idx_coulomb_integrals(k,p,h) - tc_2e_3idx_exchange_integrals(k,p,h) enddo fock_op_2_e_tc_closed_shell(p,h) = accu enddo enddo ! virt ---> virt single excitations do h0 = 1, n_occ_ab_virt(1) h=occ_virt(h0,1) do p0 = 1, n_occ_ab_virt(1) p = occ_virt(p0,1) accu = 0.d0 do k0 = 1, n_occ_ab(1) k = occ(k0,1) accu += 2.d0 * tc_2e_3idx_coulomb_integrals(k,p,h) - tc_2e_3idx_exchange_integrals(k,p,h) enddo fock_op_2_e_tc_closed_shell(p,h) = accu enddo enddo do h0 = 1, n_occ_ab_virt(1) h = occ_virt(h0,1) do p0 = 1, n_occ_ab_virt(1) p=occ_virt(p0,1) accu = 0.d0 do k0 = 1, n_occ_ab(1) k = occ(k0,1) accu += 2.d0 * tc_2e_3idx_coulomb_integrals(k,p,h) - tc_2e_3idx_exchange_integrals(k,p,h) enddo fock_op_2_e_tc_closed_shell(p,h) = accu enddo enddo ! docc ---> docc single excitations do h0 = 1, n_occ_ab(1) h=occ(h0,1) do p0 = 1, n_occ_ab(1) p = occ(p0,1) accu = 0.d0 do k0 = 1, n_occ_ab(1) k = occ(k0,1) accu += 2.d0 * tc_2e_3idx_coulomb_integrals(k,p,h) - tc_2e_3idx_exchange_integrals(k,p,h) enddo fock_op_2_e_tc_closed_shell(p,h) = accu enddo enddo do h0 = 1, n_occ_ab(1) h = occ(h0,1) do p0 = 1, n_occ_ab(1) p=occ(p0,1) accu = 0.d0 do k0 = 1, n_occ_ab(1) k = occ(k0,1) accu += 2.d0 * tc_2e_3idx_coulomb_integrals(k,p,h) - tc_2e_3idx_exchange_integrals(k,p,h) enddo fock_op_2_e_tc_closed_shell(p,h) = accu enddo enddo ! do i = 1, mo_num ! write(*,'(100(F10.5,X))')fock_op_2_e_tc_closed_shell(:,i) ! enddo END_PROVIDER ! --- subroutine single_htilde_mu_mat_fock_bi_ortho_no_3e(Nint, key_j, key_i, htot) BEGIN_DOC ! for single excitation ONLY FOR ONE- AND TWO-BODY TERMS !! !! WARNING !! ! ! Non hermitian !! END_DOC use bitmasks implicit none integer, intent(in) :: Nint integer(bit_kind), intent(in) :: key_j(Nint,2), key_i(Nint,2) double precision, intent(out) :: htot double precision :: hmono, htwoe integer :: occ(Nint*bit_kind_size,2) integer :: Ne(2), i, j, ii, jj, ispin, jspin, k, kk integer :: degree,exc(0:2,2,2) integer :: h1, p1, h2, p2, s1, s2 double precision :: get_mo_two_e_integral_tc_int, phase double precision :: direct_int, exchange_int_12, exchange_int_23, exchange_int_13 integer :: other_spin(2) integer(bit_kind) :: key_j_core(Nint,2), key_i_core(Nint,2) other_spin(1) = 2 other_spin(2) = 1 hmono = 0.d0 htwoe = 0.d0 htot = 0.d0 call get_excitation_degree(key_i, key_j, degree, Nint) if(degree.ne.1)then return endif call bitstring_to_list_ab(key_i, occ, Ne, Nint) call get_single_excitation(key_i, key_j, exc, phase, Nint) call decode_exc(exc,1,h1,p1,h2,p2,s1,s2) call get_single_excitation_from_fock_tc_no_3e(Nint, key_i, key_j, h1, p1, s1, phase, hmono, htwoe, htot) end ! --- subroutine get_single_excitation_from_fock_tc_no_3e(Nint, key_i, key_j, h, p, spin, phase, hmono, htwoe, htot) use bitmasks implicit none integer, intent(in) :: Nint integer, intent(in) :: h, p, spin double precision, intent(in) :: phase integer(bit_kind), intent(in) :: key_i(Nint,2), key_j(Nint,2) double precision, intent(out) :: hmono,htwoe,htot integer(bit_kind) :: differences(Nint,2) integer(bit_kind) :: hole(Nint,2) integer(bit_kind) :: partcl(Nint,2) integer :: occ_hole(Nint*bit_kind_size,2) integer :: occ_partcl(Nint*bit_kind_size,2) integer :: n_occ_ab_hole(2),n_occ_ab_partcl(2) integer :: i0,i double precision :: buffer_c(mo_num), buffer_x(mo_num) do i = 1, mo_num buffer_c(i) = tc_2e_3idx_coulomb_integrals(i,p,h) buffer_x(i) = tc_2e_3idx_exchange_integrals(i,p,h) enddo do i = 1, Nint differences(i,1) = xor(key_i(i,1),ref_closed_shell_bitmask(i,1)) differences(i,2) = xor(key_i(i,2),ref_closed_shell_bitmask(i,2)) hole(i,1) = iand(differences(i,1),ref_closed_shell_bitmask(i,1)) hole(i,2) = iand(differences(i,2),ref_closed_shell_bitmask(i,2)) partcl(i,1) = iand(differences(i,1),key_i(i,1)) partcl(i,2) = iand(differences(i,2),key_i(i,2)) enddo call bitstring_to_list_ab(hole, occ_hole, n_occ_ab_hole, Nint) call bitstring_to_list_ab(partcl, occ_partcl, n_occ_ab_partcl, Nint) hmono = mo_bi_ortho_tc_one_e(p,h) htwoe = fock_op_2_e_tc_closed_shell(p,h) ! holes :: direct terms do i0 = 1, n_occ_ab_hole(1) i = occ_hole(i0,1) htwoe -= buffer_c(i) enddo do i0 = 1, n_occ_ab_hole(2) i = occ_hole(i0,2) htwoe -= buffer_c(i) enddo ! holes :: exchange terms do i0 = 1, n_occ_ab_hole(spin) i = occ_hole(i0,spin) htwoe += buffer_x(i) enddo ! particles :: direct terms do i0 = 1, n_occ_ab_partcl(1) i = occ_partcl(i0,1) htwoe += buffer_c(i) enddo do i0 = 1, n_occ_ab_partcl(2) i = occ_partcl(i0,2) htwoe += buffer_c(i) enddo ! particles :: exchange terms do i0 = 1, n_occ_ab_partcl(spin) i = occ_partcl(i0,spin) htwoe -= buffer_x(i) enddo htwoe = htwoe * phase hmono = hmono * phase htot = htwoe + hmono end