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Merge branch 'dev-stable' of https://github.com/QuantumPackage/qp2 into dev-stable

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This commit is contained in:
Anthony Scemama 2023-08-21 09:56:09 +02:00
commit 2201733dbe
57 changed files with 4670 additions and 126 deletions
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2
.github/workflows/configuration.yml vendored
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@ -22,7 +22,7 @@ jobs:
- uses: actions/checkout@v3
- name: Install dependencies
run: |
sudo apt install gfortran gcc liblapack-dev libblas-dev wget python3 make m4 pkg-config hdf5
sudo apt install gfortran gcc liblapack-dev libblas-dev wget python3 make m4 pkg-config libhdf5-dev
- name: zlib
run: |
./configure -i zlib || echo OK

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src/casscf_cipsi/50.casscf.bats Normal file
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#!/usr/bin/env bats
source $QP_ROOT/tests/bats/common.bats.sh
source $QP_ROOT/quantum_package.rc
function run_stoch() {
thresh=$2
test_exe casscf || skip
qp set perturbation do_pt2 True
qp set determinants n_det_max $3
qp set davidson threshold_davidson 1.e-10
qp set davidson n_states_diag 4
qp run casscf | tee casscf.out
energy1="$(ezfio get casscf energy_pt2 | tr '[]' ' ' | cut -d ',' -f 1)"
eq $energy1 $1 $thresh
}
@test "F2" { # 18.0198s
rm -rf f2_casscf
qp_create_ezfio -b aug-cc-pvdz ../input/f2.zmt -o f2_casscf
qp set_file f2_casscf
qp run scf
qp set_mo_class --core="[1-6,8-9]" --act="[7,10]" --virt="[11-46]"
run_stoch -198.773366970 1.e-4 100000
}
@test "N2" { # 18.0198s
rm -rf n2_casscf
qp_create_ezfio -b aug-cc-pvdz ../input/n2.xyz -o n2_casscf
qp set_file n2_casscf
qp run scf
qp set_mo_class --core="[1-4]" --act="[5-10]" --virt="[11-46]"
run_stoch -109.0961643162 1.e-4 100000
}
@test "N2_stretched" {
rm -rf n2_stretched_casscf
qp_create_ezfio -b aug-cc-pvdz -m 7 ../input/n2_stretched.xyz -o n2_stretched_casscf
qp set_file n2_stretched_casscf
qp run scf | tee scf.out
qp set_mo_class --core="[1-4]" --act="[5-10]" --virt="[11-46]"
qp set electrons elec_alpha_num 7
qp set electrons elec_beta_num 7
run_stoch -108.7860471300 1.e-4 100000
#
}

75
src/casscf_cipsi/EZFIO.cfg Normal file
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[energy]
type: double precision
doc: Calculated Selected |FCI| energy
interface: ezfio
size: (determinants.n_states)
[energy_pt2]
type: double precision
doc: Calculated |FCI| energy + |PT2|
interface: ezfio
size: (determinants.n_states)
[state_following_casscf]
type: logical
doc: If |true|, the CASSCF will try to follow the guess CI vector and orbitals
interface: ezfio,provider,ocaml
default: False
[diag_hess_cas]
type: logical
doc: If |true|, only the DIAGONAL part of the hessian is retained for the CASSCF
interface: ezfio,provider,ocaml
default: False
[hess_cv_cv]
type: logical
doc: If |true|, the core-virtual - core-virtual part of the hessian is computed
interface: ezfio,provider,ocaml
default: True
[level_shift_casscf]
type: Positive_float
doc: Energy shift on the virtual MOs to improve SCF convergence
interface: ezfio,provider,ocaml
default: 0.005
[fast_2rdm]
type: logical
doc: If true, the two-rdm are computed with a fast algo
interface: ezfio,provider,ocaml
default: True
[criterion_casscf]
type: character*(32)
doc: choice of the criterion for the convergence of the casscf: can be energy or gradients or e_pt2
interface: ezfio, provider, ocaml
default: e_pt2
[thresh_casscf]
type: Threshold
doc: Threshold on the convergence of the CASCF energy.
interface: ezfio,provider,ocaml
default: 1.e-06
[pt2_min_casscf]
type: Threshold
doc: Minimum value of the pt2_max parameter for the CIPSI in the CASSCF iterations.
interface: ezfio,provider,ocaml
default: 1.e-04
[n_big_act_orb]
type: integer
doc: Number of active orbitals from which the active space is considered as large, and therefore pt2_min_casscf is activated.
interface: ezfio,provider,ocaml
default: 16
[adaptive_pt2_max]
type: logical
doc: If |true|, the pt2_max value in the CIPSI iterations will automatically adapt, otherwise it is fixed at the value given in the EZFIO folder
interface: ezfio,provider,ocaml
default: True

5
src/casscf_cipsi/NEED Normal file
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@ -0,0 +1,5 @@
cipsi
selectors_full
generators_cas
two_body_rdm
dav_general_mat

5
src/casscf_cipsi/README.rst Normal file
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@ -0,0 +1,5 @@
======
casscf
======
|CASSCF| program with the CIPSI algorithm.

6
src/casscf_cipsi/bavard.irp.f Normal file
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@ -0,0 +1,6 @@
! -*- F90 -*-
BEGIN_PROVIDER [logical, bavard]
! bavard=.true.
bavard=.false.
END_PROVIDER

155
src/casscf_cipsi/bielec.irp.f Normal file
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BEGIN_PROVIDER [real*8, bielec_PQxx, (mo_num, mo_num,n_core_inact_act_orb,n_core_inact_act_orb)]
BEGIN_DOC
! bielec_PQxx : integral (pq|xx) with p,q arbitrary, x core or active
! indices are unshifted orbital numbers
END_DOC
implicit none
integer :: i,j,ii,jj,p,q,i3,j3,t3,v3
real*8 :: mo_two_e_integral
bielec_PQxx(:,:,:,:) = 0.d0
PROVIDE mo_two_e_integrals_in_map
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP PRIVATE(i,ii,j,jj,i3,j3) &
!$OMP SHARED(n_core_inact_orb,list_core_inact,mo_num,bielec_PQxx, &
!$OMP n_act_orb,mo_integrals_map,list_act)
!$OMP DO
do i=1,n_core_inact_orb
ii=list_core_inact(i)
do j=i,n_core_inact_orb
jj=list_core_inact(j)
call get_mo_two_e_integrals_i1j1(ii,jj,mo_num,bielec_PQxx(1,1,i,j),mo_integrals_map)
bielec_PQxx(:,:,j,i)=bielec_PQxx(:,:,i,j)
end do
do j=1,n_act_orb
jj=list_act(j)
j3=j+n_core_inact_orb
call get_mo_two_e_integrals_i1j1(ii,jj,mo_num,bielec_PQxx(1,1,i,j3),mo_integrals_map)
bielec_PQxx(:,:,j3,i)=bielec_PQxx(:,:,i,j3)
end do
end do
!$OMP END DO
!$OMP DO
do i=1,n_act_orb
ii=list_act(i)
i3=i+n_core_inact_orb
do j=i,n_act_orb
jj=list_act(j)
j3=j+n_core_inact_orb
call get_mo_two_e_integrals_i1j1(ii,jj,mo_num,bielec_PQxx(1,1,i3,j3),mo_integrals_map)
bielec_PQxx(:,:,j3,i3)=bielec_PQxx(:,:,i3,j3)
end do
end do
!$OMP END DO
!$OMP END PARALLEL
END_PROVIDER
BEGIN_PROVIDER [real*8, bielec_PxxQ, (mo_num,n_core_inact_act_orb,n_core_inact_act_orb, mo_num)]
BEGIN_DOC
! bielec_PxxQ : integral (px|xq) with p,q arbitrary, x core or active
! indices are unshifted orbital numbers
END_DOC
implicit none
integer :: i,j,ii,jj,p,q,i3,j3,t3,v3
double precision, allocatable :: integrals_array(:,:)
real*8 :: mo_two_e_integral
PROVIDE mo_two_e_integrals_in_map
bielec_PxxQ = 0.d0
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP PRIVATE(i,ii,j,jj,i3,j3,integrals_array) &
!$OMP SHARED(n_core_inact_orb,list_core_inact,mo_num,bielec_PxxQ, &
!$OMP n_act_orb,mo_integrals_map,list_act)
allocate(integrals_array(mo_num,mo_num))
!$OMP DO
do i=1,n_core_inact_orb
ii=list_core_inact(i)
do j=i,n_core_inact_orb
jj=list_core_inact(j)
call get_mo_two_e_integrals_ij(ii,jj,mo_num,integrals_array,mo_integrals_map)
do q=1,mo_num
do p=1,mo_num
bielec_PxxQ(p,i,j,q)=integrals_array(p,q)
bielec_PxxQ(p,j,i,q)=integrals_array(q,p)
end do
end do
end do
do j=1,n_act_orb
jj=list_act(j)
j3=j+n_core_inact_orb
call get_mo_two_e_integrals_ij(ii,jj,mo_num,integrals_array,mo_integrals_map)
do q=1,mo_num
do p=1,mo_num
bielec_PxxQ(p,i,j3,q)=integrals_array(p,q)
bielec_PxxQ(p,j3,i,q)=integrals_array(q,p)
end do
end do
end do
end do
!$OMP END DO
! (ip|qj)
!$OMP DO
do i=1,n_act_orb
ii=list_act(i)
i3=i+n_core_inact_orb
do j=i,n_act_orb
jj=list_act(j)
j3=j+n_core_inact_orb
call get_mo_two_e_integrals_ij(ii,jj,mo_num,integrals_array,mo_integrals_map)
do q=1,mo_num
do p=1,mo_num
bielec_PxxQ(p,i3,j3,q)=integrals_array(p,q)
bielec_PxxQ(p,j3,i3,q)=integrals_array(q,p)
end do
end do
end do
end do
!$OMP END DO
deallocate(integrals_array)
!$OMP END PARALLEL
END_PROVIDER
BEGIN_PROVIDER [real*8, bielecCI, (n_act_orb,n_act_orb,n_act_orb, mo_num)]
BEGIN_DOC
! bielecCI : integrals (tu|vp) with p arbitrary, tuv active
! index p runs over the whole basis, t,u,v only over the active orbitals
END_DOC
implicit none
integer :: i,j,k,p,t,u,v
double precision, external :: mo_two_e_integral
PROVIDE mo_two_e_integrals_in_map
!$OMP PARALLEL DO DEFAULT(NONE) &
!$OMP PRIVATE(i,j,k,p,t,u,v) &
!$OMP SHARED(mo_num,n_act_orb,list_act,bielecCI)
do p=1,mo_num
do j=1,n_act_orb
u=list_act(j)
do k=1,n_act_orb
v=list_act(k)
do i=1,n_act_orb
t=list_act(i)
bielecCI(i,k,j,p) = mo_two_e_integral(t,u,v,p)
end do
end do
end do
end do
!$OMP END PARALLEL DO
END_PROVIDER

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src/casscf_cipsi/bielec_natorb.irp.f Normal file
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BEGIN_PROVIDER [real*8, bielec_PQxx_no, (mo_num, mo_num,n_core_inact_act_orb,n_core_inact_act_orb)]
BEGIN_DOC
! integral (pq|xx) in the basis of natural MOs
! indices are unshifted orbital numbers
END_DOC
implicit none
integer :: i,j,k,l,t,u,p,q
double precision, allocatable :: f(:,:,:), d(:,:,:)
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP PRIVATE(j,k,l,p,d,f) &
!$OMP SHARED(n_core_inact_act_orb,mo_num,n_act_orb,n_core_inact_orb, &
!$OMP bielec_PQxx_no,bielec_PQxx,list_act,natorbsCI)
allocate (f(n_act_orb,mo_num,n_core_inact_act_orb), &
d(n_act_orb,mo_num,n_core_inact_act_orb))
!$OMP DO
do l=1,n_core_inact_act_orb
bielec_PQxx_no(:,:,:,l) = bielec_PQxx(:,:,:,l)
do k=1,n_core_inact_act_orb
do j=1,mo_num
do p=1,n_act_orb
f(p,j,k)=bielec_PQxx_no(list_act(p),j,k,l)
end do
end do
end do
call dgemm('T','N',n_act_orb,mo_num*n_core_inact_act_orb,n_act_orb,1.d0, &
natorbsCI, size(natorbsCI,1), &
f, n_act_orb, &
0.d0, &
d, n_act_orb)
do k=1,n_core_inact_act_orb
do j=1,mo_num
do p=1,n_act_orb
bielec_PQxx_no(list_act(p),j,k,l)=d(p,j,k)
end do
end do
do j=1,mo_num
do p=1,n_act_orb
f(p,j,k)=bielec_PQxx_no(j,list_act(p),k,l)
end do
end do
end do
call dgemm('T','N',n_act_orb,mo_num*n_core_inact_act_orb,n_act_orb,1.d0, &
natorbsCI, n_act_orb, &
f, n_act_orb, &
0.d0, &
d, n_act_orb)
do k=1,n_core_inact_act_orb
do p=1,n_act_orb
do j=1,mo_num
bielec_PQxx_no(j,list_act(p),k,l)=d(p,j,k)
end do
end do
end do
end do
!$OMP END DO NOWAIT
deallocate (f,d)
allocate (f(mo_num,mo_num,n_act_orb),d(mo_num,mo_num,n_act_orb))
!$OMP DO
do l=1,n_core_inact_act_orb
do p=1,n_act_orb
do k=1,mo_num
do j=1,mo_num
f(j,k,p) = bielec_PQxx_no(j,k,n_core_inact_orb+p,l)
end do
end do
end do
call dgemm('N','N',mo_num*mo_num,n_act_orb,n_act_orb,1.d0, &
f, mo_num*mo_num, &
natorbsCI, n_act_orb, &
0.d0, &
d, mo_num*mo_num)
do p=1,n_act_orb
do k=1,mo_num
do j=1,mo_num
bielec_PQxx_no(j,k,n_core_inact_orb+p,l)=d(j,k,p)
end do
end do
end do
end do
!$OMP END DO NOWAIT
!$OMP BARRIER
!$OMP DO
do l=1,n_core_inact_act_orb
do p=1,n_act_orb
do k=1,mo_num
do j=1,mo_num
f(j,k,p) = bielec_PQxx_no(j,k,l,n_core_inact_orb+p)
end do
end do
end do
call dgemm('N','N',mo_num*mo_num,n_act_orb,n_act_orb,1.d0, &
f, mo_num*mo_num, &
natorbsCI, n_act_orb, &
0.d0, &
d, mo_num*mo_num)
do p=1,n_act_orb
do k=1,mo_num
do j=1,mo_num
bielec_PQxx_no(j,k,l,n_core_inact_orb+p)=d(j,k,p)
end do
end do
end do
end do
!$OMP END DO
deallocate (f,d)
!$OMP END PARALLEL
END_PROVIDER
BEGIN_PROVIDER [real*8, bielec_PxxQ_no, (mo_num,n_core_inact_act_orb,n_core_inact_act_orb, mo_num)]
BEGIN_DOC
! integral (px|xq) in the basis of natural MOs
! indices are unshifted orbital numbers
END_DOC
implicit none
integer :: i,j,k,l,t,u,p,q
double precision, allocatable :: f(:,:,:), d(:,:,:)
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP PRIVATE(j,k,l,p,d,f) &
!$OMP SHARED(n_core_inact_act_orb,mo_num,n_act_orb,n_core_inact_orb, &
!$OMP bielec_PxxQ_no,bielec_PxxQ,list_act,natorbsCI)
allocate (f(n_act_orb,n_core_inact_act_orb,n_core_inact_act_orb), &
d(n_act_orb,n_core_inact_act_orb,n_core_inact_act_orb))
!$OMP DO
do j=1,mo_num
bielec_PxxQ_no(:,:,:,j) = bielec_PxxQ(:,:,:,j)
do l=1,n_core_inact_act_orb
do k=1,n_core_inact_act_orb
do p=1,n_act_orb
f(p,k,l) = bielec_PxxQ_no(list_act(p),k,l,j)
end do
end do
end do
call dgemm('T','N',n_act_orb,n_core_inact_act_orb**2,n_act_orb,1.d0, &
natorbsCI, size(natorbsCI,1), &
f, n_act_orb, &
0.d0, &
d, n_act_orb)
do l=1,n_core_inact_act_orb
do k=1,n_core_inact_act_orb
do p=1,n_act_orb
bielec_PxxQ_no(list_act(p),k,l,j)=d(p,k,l)
end do
end do
end do
end do
!$OMP END DO NOWAIT
deallocate (f,d)
allocate (f(n_act_orb,mo_num,n_core_inact_act_orb), &
d(n_act_orb,mo_num,n_core_inact_act_orb))
!$OMP DO
do k=1,mo_num
do l=1,n_core_inact_act_orb
do j=1,mo_num
do p=1,n_act_orb
f(p,j,l) = bielec_PxxQ_no(j,n_core_inact_orb+p,l,k)
end do
end do
end do
call dgemm('T','N',n_act_orb,mo_num*n_core_inact_act_orb,n_act_orb,1.d0, &
natorbsCI, size(natorbsCI,1), &
f, n_act_orb, &
0.d0, &
d, n_act_orb)
do l=1,n_core_inact_act_orb
do j=1,mo_num
do p=1,n_act_orb
bielec_PxxQ_no(j,n_core_inact_orb+p,l,k)=d(p,j,l)
end do
end do
end do
end do
!$OMP END DO NOWAIT
deallocate(f,d)
allocate(f(mo_num,n_core_inact_act_orb,n_act_orb), &
d(mo_num,n_core_inact_act_orb,n_act_orb) )
!$OMP DO
do k=1,mo_num
do p=1,n_act_orb
do l=1,n_core_inact_act_orb
do j=1,mo_num
f(j,l,p) = bielec_PxxQ_no(j,l,n_core_inact_orb+p,k)
end do
end do
end do
call dgemm('N','N',mo_num*n_core_inact_act_orb,n_act_orb,n_act_orb,1.d0, &
f, mo_num*n_core_inact_act_orb, &
natorbsCI, size(natorbsCI,1), &
0.d0, &
d, mo_num*n_core_inact_act_orb)
do p=1,n_act_orb
do l=1,n_core_inact_act_orb
do j=1,mo_num
bielec_PxxQ_no(j,l,n_core_inact_orb+p,k)=d(j,l,p)
end do
end do
end do
end do
!$OMP END DO NOWAIT
!$OMP BARRIER
!$OMP DO
do l=1,n_core_inact_act_orb
do p=1,n_act_orb
do k=1,n_core_inact_act_orb
do j=1,mo_num
f(j,k,p) = bielec_PxxQ_no(j,k,l,n_core_inact_orb+p)
end do
end do
end do
call dgemm('N','N',mo_num*n_core_inact_act_orb,n_act_orb,n_act_orb,1.d0, &
f, mo_num*n_core_inact_act_orb, &
natorbsCI, size(natorbsCI,1), &
0.d0, &
d, mo_num*n_core_inact_act_orb)
do p=1,n_act_orb
do k=1,n_core_inact_act_orb
do j=1,mo_num
bielec_PxxQ_no(j,k,l,n_core_inact_orb+p)=d(j,k,p)
end do
end do
end do
end do
!$OMP END DO NOWAIT
deallocate(f,d)
!$OMP END PARALLEL
END_PROVIDER
BEGIN_PROVIDER [real*8, bielecCI_no, (n_act_orb,n_act_orb,n_act_orb, mo_num)]
BEGIN_DOC
! integrals (tu|vp) in the basis of natural MOs
! index p runs over the whole basis, t,u,v only over the active orbitals
END_DOC
implicit none
integer :: i,j,k,l,t,u,p,q
double precision, allocatable :: f(:,:,:), d(:,:,:)
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP PRIVATE(j,k,l,p,d,f) &
!$OMP SHARED(n_core_inact_act_orb,mo_num,n_act_orb,n_core_inact_orb, &
!$OMP bielecCI_no,bielecCI,list_act,natorbsCI)
allocate (f(n_act_orb,n_act_orb,mo_num), &
d(n_act_orb,n_act_orb,mo_num))
!$OMP DO
do l=1,mo_num
bielecCI_no(:,:,:,l) = bielecCI(:,:,:,l)
do k=1,n_act_orb
do j=1,n_act_orb
do p=1,n_act_orb
f(p,j,k)=bielecCI_no(p,j,k,l)
end do
end do
end do
call dgemm('T','N',n_act_orb,n_act_orb*n_act_orb,n_act_orb,1.d0, &
natorbsCI, size(natorbsCI,1), &
f, n_act_orb, &
0.d0, &
d, n_act_orb)
do k=1,n_act_orb
do j=1,n_act_orb
do p=1,n_act_orb
bielecCI_no(p,j,k,l)=d(p,j,k)
end do
end do
do j=1,n_act_orb
do p=1,n_act_orb
f(p,j,k)=bielecCI_no(j,p,k,l)
end do
end do
end do
call dgemm('T','N',n_act_orb,n_act_orb*n_act_orb,n_act_orb,1.d0, &
natorbsCI, n_act_orb, &
f, n_act_orb, &
0.d0, &
d, n_act_orb)
do k=1,n_act_orb
do p=1,n_act_orb
do j=1,n_act_orb
bielecCI_no(j,p,k,l)=d(p,j,k)
end do
end do
end do
do p=1,n_act_orb
do k=1,n_act_orb
do j=1,n_act_orb
f(j,k,p)=bielecCI_no(j,k,p,l)
end do
end do
end do
call dgemm('N','N',n_act_orb*n_act_orb,n_act_orb,n_act_orb,1.d0, &
f, n_act_orb*n_act_orb, &
natorbsCI, n_act_orb, &
0.d0, &
d, n_act_orb*n_act_orb)
do p=1,n_act_orb
do k=1,n_act_orb
do j=1,n_act_orb
bielecCI_no(j,k,p,l)=d(j,k,p)
end do
end do
end do
end do
!$OMP END DO
!$OMP DO
do l=1,n_act_orb
do p=1,n_act_orb
do k=1,n_act_orb
do j=1,n_act_orb
f(j,k,p)=bielecCI_no(j,k,l,list_act(p))
end do
end do
end do
call dgemm('N','N',n_act_orb*n_act_orb,n_act_orb,n_act_orb,1.d0, &
f, n_act_orb*n_act_orb, &
natorbsCI, n_act_orb, &
0.d0, &
d, n_act_orb*n_act_orb)
do p=1,n_act_orb
do k=1,n_act_orb
do j=1,n_act_orb
bielecCI_no(j,k,l,list_act(p))=d(j,k,p)
end do
end do
end do
end do
!$OMP END DO
deallocate(d,f)
!$OMP END PARALLEL
END_PROVIDER

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program casscf
implicit none
BEGIN_DOC
! TODO : Put the documentation of the program here
END_DOC
call reorder_orbitals_for_casscf
! no_vvvv_integrals = .True.
! touch no_vvvv_integrals
n_det_max_full = 500
touch n_det_max_full
pt2_relative_error = 0.04
touch pt2_relative_error
! call run_stochastic_cipsi
call run
end
subroutine run
implicit none
double precision :: energy_old, energy, pt2_max_before, ept2_before,delta_E
logical :: converged,state_following_casscf_cipsi_save
integer :: iteration
converged = .False.
energy = 0.d0
mo_label = "MCSCF"
iteration = 1
state_following_casscf_cipsi_save = state_following_casscf
state_following_casscf = .True.
touch state_following_casscf
ept2_before = 0.d0
if(adaptive_pt2_max)then
pt2_max = 0.005
SOFT_TOUCH pt2_max
endif
do while (.not.converged)
print*,'pt2_max = ',pt2_max
call run_stochastic_cipsi
energy_old = energy
energy = eone+etwo+ecore
pt2_max_before = pt2_max
call write_time(6)
call write_int(6,iteration,'CAS-SCF iteration = ')
call write_double(6,energy,'CAS-SCF energy = ')
if(n_states == 1)then
double precision :: E_PT2, PT2
call ezfio_get_casscf_cipsi_energy_pt2(E_PT2)
call ezfio_get_casscf_cipsi_energy(PT2)
PT2 -= E_PT2
call write_double(6,E_PT2,'E + PT2 energy = ')
call write_double(6,PT2,' PT2 = ')
call write_double(6,pt2_max,' PT2_MAX = ')
endif
print*,''
call write_double(6,norm_grad_vec2,'Norm of gradients = ')
call write_double(6,norm_grad_vec2_tab(1), ' Core-active gradients = ')
call write_double(6,norm_grad_vec2_tab(2), ' Core-virtual gradients = ')
call write_double(6,norm_grad_vec2_tab(3), ' Active-virtual gradients = ')
print*,''
call write_double(6,energy_improvement, 'Predicted energy improvement = ')
if(criterion_casscf == "energy")then
converged = dabs(energy_improvement) < thresh_scf
else if (criterion_casscf == "gradients")then
converged = norm_grad_vec2 < thresh_scf
else if (criterion_casscf == "e_pt2")then
delta_E = dabs(E_PT2 - ept2_before)
converged = dabs(delta_E) < thresh_casscf
endif
ept2_before = E_PT2
if(adaptive_pt2_max)then
pt2_max = dabs(energy_improvement / (pt2_relative_error))
pt2_max = min(pt2_max, pt2_max_before)
if(n_act_orb.ge.n_big_act_orb)then
pt2_max = max(pt2_max,pt2_min_casscf)
endif
endif
print*,''
call write_double(6,pt2_max, 'PT2_MAX for next iteration = ')
mo_coef = NewOrbs
mo_occ = occnum
call save_mos
if(.not.converged)then
iteration += 1
if(norm_grad_vec2.gt.0.01d0)then
N_det = N_states
else
N_det = max(N_det/8 ,N_states)
endif
psi_det = psi_det_sorted
psi_coef = psi_coef_sorted
read_wf = .True.
call clear_mo_map
SOFT_TOUCH mo_coef N_det psi_det psi_coef
if(adaptive_pt2_max)then
SOFT_TOUCH pt2_max
endif
if(iteration .gt. 3)then
state_following_casscf = state_following_casscf_cipsi_save
soft_touch state_following_casscf
endif
endif
enddo
end

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BEGIN_PROVIDER [ logical, do_only_1h1p ]
&BEGIN_PROVIDER [ logical, do_only_cas ]
&BEGIN_PROVIDER [ logical, do_ddci ]
implicit none
BEGIN_DOC
! In the CAS case, all those are always false except do_only_cas
END_DOC
do_only_cas = .True.
do_only_1h1p = .False.
do_ddci = .False.
END_PROVIDER

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subroutine davidson_diag_sx_mat(N_st, u_in, energies)
implicit none
integer, intent(in) :: N_st
double precision, intent(out) :: u_in(nMonoEx+1,n_states_diag), energies(N_st)
integer :: i,j,N_st_tmp, dim_in, sze, N_st_diag_in
integer, allocatable :: list_guess(:)
double precision, allocatable :: H_jj(:)
logical :: converged
N_st_diag_in = n_states_diag
provide SXmatrix
sze = nMonoEx+1
dim_in = sze
allocate(H_jj(sze), list_guess(sze))
H_jj(1) = 0.d0
N_st_tmp = 1
list_guess(1) = 1
do j = 2, nMonoEx+1
H_jj(j) = SXmatrix(j,j)
if(H_jj(j).lt.0.d0)then
list_guess(N_st_tmp) = j
N_st_tmp += 1
endif
enddo
if(N_st_tmp .ne. N_st)then
print*,'Pb in davidson_diag_sx_mat'
print*,'N_st_tmp .ne. N_st'
print*,N_st_tmp, N_st
stop
endif
print*,'Number of possibly interesting states = ',N_st
print*,'Corresponding diagonal elements of the SX matrix '
u_in = 0.d0
do i = 1, min(N_st, N_st_diag_in)
! do i = 1, N_st
j = list_guess(i)
print*,'i,j',i,j
print*,'SX(i,i) = ',H_jj(j)
u_in(j,i) = 1.d0
enddo
call davidson_general(u_in,H_jj,energies,dim_in,sze,N_st,N_st_diag_in,converged,SXmatrix)
print*,'energies = ',energies
end

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use bitmasks
BEGIN_PROVIDER [real*8, D0tu, (n_act_orb,n_act_orb) ]
implicit none
BEGIN_DOC
! the first-order density matrix in the basis of the starting MOs.
! matrix is state averaged.
END_DOC
integer :: t,u
do u=1,n_act_orb
do t=1,n_act_orb
D0tu(t,u) = one_e_dm_mo_alpha_average( list_act(t), list_act(u) ) + &
one_e_dm_mo_beta_average ( list_act(t), list_act(u) )
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [real*8, P0tuvx, (n_act_orb,n_act_orb,n_act_orb,n_act_orb) ]
BEGIN_DOC
! The second-order density matrix in the basis of the starting MOs ONLY IN THE RANGE OF ACTIVE MOS
! The values are state averaged
!
! We use the spin-free generators of mono-excitations
! E_pq destroys q and creates p
! D_pq = <0|E_pq|0> = D_qp
! P_pqrs = 1/2 <0|E_pq E_rs - delta_qr E_ps|0>
!
! P0tuvx(p,q,r,s) = chemist notation : 1/2 <0|E_pq E_rs - delta_qr E_ps|0>
END_DOC
implicit none
integer :: t,u,v,x
integer :: tt,uu,vv,xx
integer :: mu,nu,istate,ispin,jspin,ihole,ipart,jhole,jpart
integer :: ierr
real*8 :: phase1,phase11,phase12,phase2,phase21,phase22
integer :: nu1,nu2,nu11,nu12,nu21,nu22
integer :: ierr1,ierr2,ierr11,ierr12,ierr21,ierr22
real*8 :: cI_mu(N_states),term
integer(bit_kind), dimension(N_int,2) :: det_mu, det_mu_ex
integer(bit_kind), dimension(N_int,2) :: det_mu_ex1, det_mu_ex11, det_mu_ex12
integer(bit_kind), dimension(N_int,2) :: det_mu_ex2, det_mu_ex21, det_mu_ex22
if (bavard) then
write(6,*) ' providing the 2 body RDM on the active part'
endif
P0tuvx= 0.d0
if(fast_2rdm)then
do istate=1,N_states
do x = 1, n_act_orb
do v = 1, n_act_orb
do u = 1, n_act_orb
do t = 1, n_act_orb
! 1 1 2 2 1 2 1 2
P0tuvx(t,u,v,x) = 0.5d0 * state_av_act_2_rdm_spin_trace_mo(t,v,u,x)
enddo
enddo
enddo
enddo
enddo
else
P0tuvx = P0tuvx_peter
endif
END_PROVIDER

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use bitmasks
BEGIN_PROVIDER [real*8, P0tuvx_peter, (n_act_orb,n_act_orb,n_act_orb,n_act_orb) ]
BEGIN_DOC
! the second-order density matrix in the basis of the starting MOs
! matrices are state averaged
!
! we use the spin-free generators of mono-excitations
! E_pq destroys q and creates p
! D_pq = <0|E_pq|0> = D_qp
! P_pqrs = 1/2 <0|E_pq E_rs - delta_qr E_ps|0>
!
END_DOC
implicit none
integer :: t,u,v,x,mu,nu,istate,ispin,jspin,ihole,ipart,jhole,jpart
integer :: ierr
real*8 :: phase1,phase11,phase12,phase2,phase21,phase22
integer :: nu1,nu2,nu11,nu12,nu21,nu22
integer :: ierr1,ierr2,ierr11,ierr12,ierr21,ierr22
real*8 :: cI_mu(N_states),term
integer(bit_kind), dimension(N_int,2) :: det_mu, det_mu_ex
integer(bit_kind), dimension(N_int,2) :: det_mu_ex1, det_mu_ex11, det_mu_ex12
integer(bit_kind), dimension(N_int,2) :: det_mu_ex2, det_mu_ex21, det_mu_ex22
if (bavard) then
write(6,*) ' providing density matrix P0'
endif
P0tuvx_peter = 0.d0
! first loop: we apply E_tu, once for D_tu, once for -P_tvvu
do mu=1,n_det
call det_extract(det_mu,mu,N_int)
do istate=1,n_states
cI_mu(istate)=psi_coef(mu,istate)
end do
do t=1,n_act_orb
ipart=list_act(t)
do u=1,n_act_orb
ihole=list_act(u)
! apply E_tu
call det_copy(det_mu,det_mu_ex1,N_int)
call det_copy(det_mu,det_mu_ex2,N_int)
call do_spinfree_mono_excitation(det_mu,det_mu_ex1 &
,det_mu_ex2,nu1,nu2,ihole,ipart,phase1,phase2,ierr1,ierr2)
! det_mu_ex1 is in the list
if (nu1.ne.-1) then
do istate=1,n_states
term=cI_mu(istate)*psi_coef(nu1,istate)*phase1
! and we fill P0_tvvu
do v=1,n_act_orb
P0tuvx_peter(t,v,v,u)-=term
end do
end do
end if
! det_mu_ex2 is in the list
if (nu2.ne.-1) then
do istate=1,n_states
term=cI_mu(istate)*psi_coef(nu2,istate)*phase2
do v=1,n_act_orb
P0tuvx_peter(t,v,v,u)-=term
end do
end do
end if
end do
end do
end do
! now we do the double excitation E_tu E_vx |0>
do mu=1,n_det
call det_extract(det_mu,mu,N_int)
do istate=1,n_states
cI_mu(istate)=psi_coef(mu,istate)
end do
do v=1,n_act_orb
ipart=list_act(v)
do x=1,n_act_orb
ihole=list_act(x)
! apply E_vx
call det_copy(det_mu,det_mu_ex1,N_int)
call det_copy(det_mu,det_mu_ex2,N_int)
call do_spinfree_mono_excitation(det_mu,det_mu_ex1 &
,det_mu_ex2,nu1,nu2,ihole,ipart,phase1,phase2,ierr1,ierr2)
! we apply E_tu to the first resultant determinant, thus E_tu E_vx |0>
if (ierr1.eq.1) then
do t=1,n_act_orb
jpart=list_act(t)
do u=1,n_act_orb
jhole=list_act(u)
call det_copy(det_mu_ex1,det_mu_ex11,N_int)
call det_copy(det_mu_ex1,det_mu_ex12,N_int)
call do_spinfree_mono_excitation(det_mu_ex1,det_mu_ex11&
,det_mu_ex12,nu11,nu12,jhole,jpart,phase11,phase12,ierr11,ierr12)
if (nu11.ne.-1) then
do istate=1,n_states
P0tuvx_peter(t,u,v,x)+=cI_mu(istate)*psi_coef(nu11,istate)&
*phase11*phase1
end do
end if
if (nu12.ne.-1) then
do istate=1,n_states
P0tuvx_peter(t,u,v,x)+=cI_mu(istate)*psi_coef(nu12,istate)&
*phase12*phase1
end do
end if
end do
end do
end if
! we apply E_tu to the second resultant determinant
if (ierr2.eq.1) then
do t=1,n_act_orb
jpart=list_act(t)
do u=1,n_act_orb
jhole=list_act(u)
call det_copy(det_mu_ex2,det_mu_ex21,N_int)
call det_copy(det_mu_ex2,det_mu_ex22,N_int)
call do_spinfree_mono_excitation(det_mu_ex2,det_mu_ex21&
,det_mu_ex22,nu21,nu22,jhole,jpart,phase21,phase22,ierr21,ierr22)
if (nu21.ne.-1) then
do istate=1,n_states
P0tuvx_peter(t,u,v,x)+=cI_mu(istate)*psi_coef(nu21,istate)&
*phase21*phase2
end do
end if
if (nu22.ne.-1) then
do istate=1,n_states
P0tuvx_peter(t,u,v,x)+=cI_mu(istate)*psi_coef(nu22,istate)&
*phase22*phase2
end do
end if
end do
end do
end if
end do
end do
end do
! we average by just dividing by the number of states
do x=1,n_act_orb
do v=1,n_act_orb
do u=1,n_act_orb
do t=1,n_act_orb
P0tuvx_peter(t,u,v,x)*=0.5D0/dble(N_states)
end do
end do
end do
end do
END_PROVIDER

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use bitmasks
subroutine do_signed_mono_excitation(key1,key2,nu,ihole,ipart, &
ispin,phase,ierr)
BEGIN_DOC
! we create the mono-excitation, and determine, if possible,
! the phase and the number in the list of determinants
END_DOC
implicit none
integer(bit_kind) :: key1(N_int,2),key2(N_int,2)
integer(bit_kind), allocatable :: keytmp(:,:)
integer :: exc(0:2,2,2),ihole,ipart,ierr,nu,ispin
real*8 :: phase
logical :: found
allocate(keytmp(N_int,2))
nu=-1
phase=1.D0
ierr=0
call det_copy(key1,key2,N_int)
! write(6,*) ' key2 before excitation ',ihole,' -> ',ipart,' spin = ',ispin
! call print_det(key2,N_int)
call do_single_excitation(key2,ihole,ipart,ispin,ierr)
! write(6,*) ' key2 after ',ihole,' -> ',ipart,' spin = ',ispin
! call print_det(key2,N_int)
! write(6,*) ' excitation ',ihole,' -> ',ipart,' gives ierr = ',ierr
if (ierr.eq.1) then
! excitation is possible
! get the phase
call get_single_excitation(key1,key2,exc,phase,N_int)
! get the number in the list
found=.false.
nu=0
!TODO BOTTLENECK
do while (.not.found)
nu+=1
if (nu.gt.N_det) then
! the determinant is possible, but not in the list
found=.true.
nu=-1
else
call det_extract(keytmp,nu,N_int)
integer :: i,ii
found=.true.
do ii=1,2
do i=1,N_int
if (keytmp(i,ii).ne.key2(i,ii)) then
found=.false.
end if
end do
end do
end if
end do
end if
!
! we found the new string, the phase, and possibly the number in the list
!
end subroutine do_signed_mono_excitation
subroutine det_extract(key,nu,Nint)
BEGIN_DOC
! extract a determinant from the list of determinants
END_DOC
implicit none
integer :: ispin,i,nu,Nint
integer(bit_kind) :: key(Nint,2)
do ispin=1,2
do i=1,Nint
key(i,ispin)=psi_det(i,ispin,nu)
end do
end do
end subroutine det_extract
subroutine det_copy(key1,key2,Nint)
use bitmasks ! you need to include the bitmasks_module.f90 features
BEGIN_DOC
! copy a determinant from key1 to key2
END_DOC
implicit none
integer :: ispin,i,Nint
integer(bit_kind) :: key1(Nint,2),key2(Nint,2)
do ispin=1,2
do i=1,Nint
key2(i,ispin)=key1(i,ispin)
end do
end do
end subroutine det_copy
subroutine do_spinfree_mono_excitation(key_in,key_out1,key_out2 &
,nu1,nu2,ihole,ipart,phase1,phase2,ierr,jerr)
BEGIN_DOC
! we create the spin-free mono-excitation E_pq=(a^+_p a_q + a^+_P a_Q)
! we may create two determinants as result
!
END_DOC
implicit none
integer(bit_kind) :: key_in(N_int,2),key_out1(N_int,2)
integer(bit_kind) :: key_out2(N_int,2)
integer :: ihole,ipart,ierr,jerr,nu1,nu2
integer :: ispin
real*8 :: phase1,phase2
! write(6,*) ' applying E_',ipart,ihole,' on determinant '
! call print_det(key_in,N_int)
! spin alpha
ispin=1
call do_signed_mono_excitation(key_in,key_out1,nu1,ihole &
,ipart,ispin,phase1,ierr)
! if (ierr.eq.1) then
! write(6,*) ' 1 result is ',nu1,phase1
! call print_det(key_out1,N_int)
! end if
! spin beta
ispin=2
call do_signed_mono_excitation(key_in,key_out2,nu2,ihole &
,ipart,ispin,phase2,jerr)
! if (jerr.eq.1) then
! write(6,*) ' 2 result is ',nu2,phase2
! call print_det(key_out2,N_int)
! end if
end subroutine do_spinfree_mono_excitation

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subroutine driver_optorb
implicit none
end

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program print_2rdm
implicit none
BEGIN_DOC
! get the active part of the bielectronic energy on a given wave function.
!
! useful to test the active part of the spin trace 2 rdms
END_DOC
!no_vvvv_integrals = .True.
read_wf = .True.
!touch read_wf no_vvvv_integrals
!call routine
!call routine_bis
call print_grad
end
subroutine print_grad
implicit none
integer :: i
do i = 1, nMonoEx
if(dabs(gradvec2(i)).gt.1.d-5)then
print*,''
print*,i,gradvec2(i),excit(:,i)
endif
enddo
end
subroutine routine
integer :: i,j,k,l
integer :: ii,jj,kk,ll
double precision :: accu(4),twodm,thr,act_twodm2,integral,get_two_e_integral
thr = 1.d-10
accu = 0.d0
do ll = 1, n_act_orb
l = list_act(ll)
do kk = 1, n_act_orb
k = list_act(kk)
do jj = 1, n_act_orb
j = list_act(jj)
do ii = 1, n_act_orb
i = list_act(ii)
integral = get_two_e_integral(i,j,k,l,mo_integrals_map)
accu(1) += state_av_act_2_rdm_spin_trace_mo(ii,jj,kk,ll) * integral
enddo
enddo
enddo
enddo
print*,'accu = ',accu(1)
end

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BEGIN_PROVIDER [real*8, gradvec_old, (nMonoEx)]
BEGIN_DOC
! calculate the orbital gradient <Psi| H E_pq |Psi> by hand, i.e. for
! each determinant I we determine the string E_pq |I> (alpha and beta
! separately) and generate <Psi|H E_pq |I>
! sum_I c_I <Psi|H E_pq |I> is then the pq component of the orbital
! gradient
! E_pq = a^+_pa_q + a^+_Pa_Q
END_DOC
implicit none
integer :: ii,tt,aa,indx,ihole,ipart,istate
real*8 :: res
do indx=1,nMonoEx
ihole=excit(1,indx)
ipart=excit(2,indx)
call calc_grad_elem(ihole,ipart,res)
gradvec_old(indx)=res
end do
real*8 :: norm_grad
norm_grad=0.d0
do indx=1,nMonoEx
norm_grad+=gradvec_old(indx)*gradvec_old(indx)
end do
norm_grad=sqrt(norm_grad)
if (bavard) then
write(6,*)
write(6,*) ' Norm of the orbital gradient (via <0|EH|0>) : ', norm_grad
write(6,*)
endif
END_PROVIDER
subroutine calc_grad_elem(ihole,ipart,res)
BEGIN_DOC
! eq 18 of Siegbahn et al, Physica Scripta 1980
! we calculate 2 <Psi| H E_pq | Psi>, q=hole, p=particle
END_DOC
implicit none
integer :: ihole,ipart,mu,iii,ispin,ierr,nu,istate
real*8 :: res
integer(bit_kind), allocatable :: det_mu(:,:),det_mu_ex(:,:)
real*8 :: i_H_psi_array(N_states),phase
allocate(det_mu(N_int,2))
allocate(det_mu_ex(N_int,2))
res=0.D0
do mu=1,n_det
! get the string of the determinant
call det_extract(det_mu,mu,N_int)
do ispin=1,2
! do the monoexcitation on it
call det_copy(det_mu,det_mu_ex,N_int)
call do_signed_mono_excitation(det_mu,det_mu_ex,nu &
,ihole,ipart,ispin,phase,ierr)
if (ierr.eq.1) then
call i_H_psi(det_mu_ex,psi_det,psi_coef,N_int &
,N_det,N_det,N_states,i_H_psi_array)
do istate=1,N_states
res+=i_H_psi_array(istate)*psi_coef(mu,istate)*phase
end do
end if
end do
end do
! state-averaged gradient
res*=2.D0/dble(N_states)
end subroutine calc_grad_elem

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use bitmasks
BEGIN_PROVIDER [ integer, nMonoEx ]
BEGIN_DOC
! Number of single excitations
END_DOC
implicit none
nMonoEx=n_core_inact_orb*n_act_orb+n_core_inact_orb*n_virt_orb+n_act_orb*n_virt_orb
END_PROVIDER
BEGIN_PROVIDER [integer, n_c_a_prov]
&BEGIN_PROVIDER [integer, n_c_v_prov]
&BEGIN_PROVIDER [integer, n_a_v_prov]
implicit none
n_c_a_prov = n_core_inact_orb * n_act_orb
n_c_v_prov = n_core_inact_orb * n_virt_orb
n_a_v_prov = n_act_orb * n_virt_orb
END_PROVIDER
BEGIN_PROVIDER [integer, excit, (2,nMonoEx)]
&BEGIN_PROVIDER [character*3, excit_class, (nMonoEx)]
&BEGIN_PROVIDER [integer, list_idx_c_a, (3,n_c_a_prov) ]
&BEGIN_PROVIDER [integer, list_idx_c_v, (3,n_c_v_prov) ]
&BEGIN_PROVIDER [integer, list_idx_a_v, (3,n_a_v_prov) ]
&BEGIN_PROVIDER [integer, mat_idx_c_a, (n_core_inact_orb,n_act_orb)
&BEGIN_PROVIDER [integer, mat_idx_c_v, (n_core_inact_orb,n_virt_orb)
&BEGIN_PROVIDER [integer, mat_idx_a_v, (n_act_orb,n_virt_orb)
BEGIN_DOC
! a list of the orbitals involved in the excitation
END_DOC
implicit none
integer :: i,t,a,ii,tt,aa,indx,indx_tmp
indx=0
indx_tmp = 0
do ii=1,n_core_inact_orb
i=list_core_inact(ii)
do tt=1,n_act_orb
t=list_act(tt)
indx+=1
excit(1,indx)=i
excit(2,indx)=t
excit_class(indx)='c-a'
indx_tmp += 1
list_idx_c_a(1,indx_tmp) = indx
list_idx_c_a(2,indx_tmp) = ii
list_idx_c_a(3,indx_tmp) = tt
mat_idx_c_a(ii,tt) = indx
end do
end do
indx_tmp = 0
do ii=1,n_core_inact_orb
i=list_core_inact(ii)
do aa=1,n_virt_orb
a=list_virt(aa)
indx+=1
excit(1,indx)=i
excit(2,indx)=a
excit_class(indx)='c-v'
indx_tmp += 1
list_idx_c_v(1,indx_tmp) = indx
list_idx_c_v(2,indx_tmp) = ii
list_idx_c_v(3,indx_tmp) = aa
mat_idx_c_v(ii,aa) = indx
end do
end do
indx_tmp = 0
do tt=1,n_act_orb
t=list_act(tt)
do aa=1,n_virt_orb
a=list_virt(aa)
indx+=1
excit(1,indx)=t
excit(2,indx)=a
excit_class(indx)='a-v'
indx_tmp += 1
list_idx_a_v(1,indx_tmp) = indx
list_idx_a_v(2,indx_tmp) = tt
list_idx_a_v(3,indx_tmp) = aa
mat_idx_a_v(tt,aa) = indx
end do
end do
if (bavard) then
write(6,*) ' Filled the table of the Monoexcitations '
do indx=1,nMonoEx
write(6,*) ' ex ',indx,' : ',excit(1,indx),' -> ' &
,excit(2,indx),' ',excit_class(indx)
end do
end if
END_PROVIDER
BEGIN_PROVIDER [real*8, gradvec2, (nMonoEx)]
&BEGIN_PROVIDER [real*8, norm_grad_vec2]
&BEGIN_PROVIDER [real*8, norm_grad_vec2_tab, (3)]
BEGIN_DOC
! calculate the orbital gradient <Psi| H E_pq |Psi> from density
! matrices and integrals; Siegbahn et al, Phys Scr 1980
! eqs 14 a,b,c
END_DOC
implicit none
integer :: i,t,a,indx
real*8 :: gradvec_it,gradvec_ia,gradvec_ta
indx=0
norm_grad_vec2_tab = 0.d0
do i=1,n_core_inact_orb
do t=1,n_act_orb
indx+=1
gradvec2(indx)=gradvec_it(i,t)
norm_grad_vec2_tab(1) += gradvec2(indx)*gradvec2(indx)
end do
end do
do i=1,n_core_inact_orb
do a=1,n_virt_orb
indx+=1
gradvec2(indx)=gradvec_ia(i,a)
norm_grad_vec2_tab(2) += gradvec2(indx)*gradvec2(indx)
end do
end do
do t=1,n_act_orb
do a=1,n_virt_orb
indx+=1
gradvec2(indx)=gradvec_ta(t,a)
norm_grad_vec2_tab(3) += gradvec2(indx)*gradvec2(indx)
end do
end do
norm_grad_vec2=0.d0
do indx=1,nMonoEx
norm_grad_vec2+=gradvec2(indx)*gradvec2(indx)
end do
do i = 1, 3
norm_grad_vec2_tab(i) = dsqrt(norm_grad_vec2_tab(i))
enddo
norm_grad_vec2=sqrt(norm_grad_vec2)
if(bavard)then
write(6,*)
write(6,*) ' Norm of the orbital gradient (via D, P and integrals): ', norm_grad_vec2
write(6,*)
endif
END_PROVIDER
real*8 function gradvec_it(i,t)
BEGIN_DOC
! the orbital gradient core/inactive -> active
! we assume natural orbitals
END_DOC
implicit none
integer :: i,t
integer :: ii,tt,v,vv,x,y
integer :: x3,y3
ii=list_core_inact(i)
tt=list_act(t)
gradvec_it=2.D0*(Fipq(tt,ii)+Fapq(tt,ii))
gradvec_it-=occnum(tt)*Fipq(ii,tt)
do v=1,n_act_orb ! active
vv=list_act(v)
do x=1,n_act_orb ! active
x3=x+n_core_inact_orb ! list_act(x)
do y=1,n_act_orb ! active
y3=y+n_core_inact_orb ! list_act(y)
! Gamma(2) a a a a 1/r12 i a a a
gradvec_it-=2.D0*P0tuvx_no(t,v,x,y)*bielec_PQxx_no(ii,vv,x3,y3)
end do
end do
end do
gradvec_it*=2.D0
end function gradvec_it
real*8 function gradvec_ia(i,a)
BEGIN_DOC
! the orbital gradient core/inactive -> virtual
END_DOC
implicit none
integer :: i,a,ii,aa
ii=list_core_inact(i)
aa=list_virt(a)
gradvec_ia=2.D0*(Fipq(aa,ii)+Fapq(aa,ii))
gradvec_ia*=2.D0
end function gradvec_ia
real*8 function gradvec_ta(t,a)
BEGIN_DOC
! the orbital gradient active -> virtual
! we assume natural orbitals
END_DOC
implicit none
integer :: t,a,tt,aa,v,vv,x,y
tt=list_act(t)
aa=list_virt(a)
gradvec_ta=0.D0
gradvec_ta+=occnum(tt)*Fipq(aa,tt)
do v=1,n_act_orb
do x=1,n_act_orb
do y=1,n_act_orb
gradvec_ta+=2.D0*P0tuvx_no(t,v,x,y)*bielecCI_no(x,y,v,aa)
end do
end do
end do
gradvec_ta*=2.D0
end function gradvec_ta

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use bitmasks
real*8 function hessmat_itju(i,t,j,u)
BEGIN_DOC
! the orbital hessian for core/inactive -> active, core/inactive -> active
! i, t, j, u are list indices, the corresponding orbitals are ii,tt,jj,uu
!
! we assume natural orbitals
END_DOC
implicit none
integer :: i,t,j,u,ii,tt,uu,v,vv,x,xx,y,jj
real*8 :: term,t2
ii=list_core_inact(i)
tt=list_act(t)
if (i.eq.j) then
if (t.eq.u) then
! diagonal element
term=occnum(tt)*Fipq(ii,ii)+2.D0*(Fipq(tt,tt)+Fapq(tt,tt)) &
-2.D0*(Fipq(ii,ii)+Fapq(ii,ii))
term+=2.D0*(3.D0*bielec_pxxq_no(tt,i,i,tt)-bielec_pqxx_no(tt,tt,i,i))
term-=2.D0*occnum(tt)*(3.D0*bielec_pxxq_no(tt,i,i,tt) &
-bielec_pqxx_no(tt,tt,i,i))
term-=occnum(tt)*Fipq(tt,tt)
do v=1,n_act_orb
vv=list_act(v)
do x=1,n_act_orb
xx=list_act(x)
term+=2.D0*(P0tuvx_no(t,t,v,x)*bielec_pqxx_no(vv,xx,i,i) &
+(P0tuvx_no(t,x,v,t)+P0tuvx_no(t,x,t,v))* &
bielec_pxxq_no(vv,i,i,xx))
do y=1,n_act_orb
term-=2.D0*P0tuvx_no(t,v,x,y)*bielecCI_no(t,v,y,xx)
end do
end do
end do
else
! it/iu, t != u
uu=list_act(u)
term=2.D0*(Fipq(tt,uu)+Fapq(tt,uu))
term+=2.D0*(4.D0*bielec_PxxQ_no(tt,i,j,uu)-bielec_PxxQ_no(uu,i,j,tt) &
-bielec_PQxx_no(tt,uu,i,j))
term-=occnum(tt)*Fipq(uu,tt)
term-=(occnum(tt)+occnum(uu)) &
*(3.D0*bielec_PxxQ_no(tt,i,i,uu)-bielec_PQxx_no(uu,tt,i,i))
do v=1,n_act_orb
vv=list_act(v)
! term-=D0tu(u,v)*Fipq(tt,vv) ! published, but inverting t and u seems more correct
do x=1,n_act_orb
xx=list_act(x)
term+=2.D0*(P0tuvx_no(u,t,v,x)*bielec_pqxx_no(vv,xx,i,i) &
+(P0tuvx_no(u,x,v,t)+P0tuvx_no(u,x,t,v)) &
*bielec_pxxq_no(vv,i,i,xx))
do y=1,n_act_orb
term-=2.D0*P0tuvx_no(t,v,x,y)*bielecCI_no(u,v,y,xx)
end do
end do
end do
end if
else
! it/ju
jj=list_core_inact(j)
uu=list_act(u)
if (t.eq.u) then
term=occnum(tt)*Fipq(ii,jj)
term-=2.D0*(Fipq(ii,jj)+Fapq(ii,jj))
else
term=0.D0
end if
term+=2.D0*(4.D0*bielec_PxxQ_no(tt,i,j,uu)-bielec_PxxQ_no(uu,i,j,tt) &
-bielec_PQxx_no(tt,uu,i,j))
term-=(occnum(tt)+occnum(uu))* &
(4.D0*bielec_PxxQ_no(tt,i,j,uu)-bielec_PxxQ_no(uu,i,j,tt) &
-bielec_PQxx_no(uu,tt,i,j))
do v=1,n_act_orb
vv=list_act(v)
do x=1,n_act_orb
xx=list_act(x)
term+=2.D0*(P0tuvx_no(u,t,v,x)*bielec_pqxx_no(vv,xx,i,j) &
+(P0tuvx_no(u,x,v,t)+P0tuvx_no(u,x,t,v)) &
*bielec_pxxq_no(vv,i,j,xx))
end do
end do
end if
term*=2.D0
hessmat_itju=term
end function hessmat_itju
real*8 function hessmat_itja(i,t,j,a)
BEGIN_DOC
! the orbital hessian for core/inactive -> active, core/inactive -> virtual
END_DOC
implicit none
integer :: i,t,j,a,ii,tt,jj,aa,v,vv,x,y
real*8 :: term
! it/ja
ii=list_core_inact(i)
tt=list_act(t)
jj=list_core_inact(j)
aa=list_virt(a)
term=2.D0*(4.D0*bielec_pxxq_no(aa,j,i,tt) &
-bielec_pqxx_no(aa,tt,i,j) -bielec_pxxq_no(aa,i,j,tt))
term-=occnum(tt)*(4.D0*bielec_pxxq_no(aa,j,i,tt) &
-bielec_pqxx_no(aa,tt,i,j) -bielec_pxxq_no(aa,i,j,tt))
if (i.eq.j) then
term+=2.D0*(Fipq(aa,tt)+Fapq(aa,tt))
term-=0.5D0*occnum(tt)*Fipq(aa,tt)
do v=1,n_act_orb
do x=1,n_act_orb
do y=1,n_act_orb
term-=P0tuvx_no(t,v,x,y)*bielecCI_no(x,y,v,aa)
end do
end do
end do
end if
term*=2.D0
hessmat_itja=term
end function hessmat_itja
real*8 function hessmat_itua(i,t,u,a)
BEGIN_DOC
! the orbital hessian for core/inactive -> active, active -> virtual
END_DOC
implicit none
integer :: i,t,u,a,ii,tt,uu,aa,v,vv,x,xx,u3,t3,v3
real*8 :: term
ii=list_core_inact(i)
tt=list_act(t)
t3=t+n_core_inact_orb
uu=list_act(u)
u3=u+n_core_inact_orb
aa=list_virt(a)
if (t.eq.u) then
term=-occnum(tt)*Fipq(aa,ii)
else
term=0.D0
end if
term-=occnum(uu)*(bielec_pqxx_no(aa,ii,t3,u3)-4.D0*bielec_pqxx_no(aa,uu,t3,i)&
+bielec_pxxq_no(aa,t3,u3,ii))
do v=1,n_act_orb
vv=list_act(v)
v3=v+n_core_inact_orb
do x=1,n_act_orb
integer :: x3
xx=list_act(x)
x3=x+n_core_inact_orb
term-=2.D0*(P0tuvx_no(t,u,v,x)*bielec_pqxx_no(aa,ii,v3,x3) &
+(P0tuvx_no(t,v,u,x)+P0tuvx_no(t,v,x,u)) &
*bielec_pqxx_no(aa,xx,v3,i))
end do
end do
if (t.eq.u) then
term+=Fipq(aa,ii)+Fapq(aa,ii)
end if
term*=2.D0
hessmat_itua=term
end function hessmat_itua
real*8 function hessmat_iajb(i,a,j,b)
BEGIN_DOC
! the orbital hessian for core/inactive -> virtual, core/inactive -> virtual
END_DOC
implicit none
integer :: i,a,j,b,ii,aa,jj,bb
real*8 :: term
ii=list_core_inact(i)
aa=list_virt(a)
if (i.eq.j) then
if (a.eq.b) then
! ia/ia
term=2.D0*(Fipq(aa,aa)+Fapq(aa,aa)-Fipq(ii,ii)-Fapq(ii,ii))
term+=2.D0*(3.D0*bielec_pxxq_no(aa,i,i,aa)-bielec_pqxx_no(aa,aa,i,i))
else
bb=list_virt(b)
! ia/ib
term=2.D0*(Fipq(aa,bb)+Fapq(aa,bb))
term+=2.D0*(3.D0*bielec_pxxq_no(aa,i,i,bb)-bielec_pqxx_no(aa,bb,i,i))
end if
else
! ia/jb
jj=list_core_inact(j)
bb=list_virt(b)
term=2.D0*(4.D0*bielec_pxxq_no(aa,i,j,bb)-bielec_pqxx_no(aa,bb,i,j) &
-bielec_pxxq_no(aa,j,i,bb))
if (a.eq.b) then
term-=2.D0*(Fipq(ii,jj)+Fapq(ii,jj))
end if
end if
term*=2.D0
hessmat_iajb=term
end function hessmat_iajb
real*8 function hessmat_iatb(i,a,t,b)
BEGIN_DOC
! the orbital hessian for core/inactive -> virtual, active -> virtual
END_DOC
implicit none
integer :: i,a,t,b,ii,aa,tt,bb,v,vv,x,y,v3,t3
real*8 :: term
ii=list_core_inact(i)
aa=list_virt(a)
tt=list_act(t)
bb=list_virt(b)
t3=t+n_core_inact_orb
term=occnum(tt)*(4.D0*bielec_pxxq_no(aa,i,t3,bb)-bielec_pxxq_no(aa,t3,i,bb)&
-bielec_pqxx_no(aa,bb,i,t3))
if (a.eq.b) then
term-=Fipq(tt,ii)+Fapq(tt,ii)
term-=0.5D0*occnum(tt)*Fipq(tt,ii)
do v=1,n_act_orb
do x=1,n_act_orb
do y=1,n_act_orb
term-=P0tuvx_no(t,v,x,y)*bielecCI_no(x,y,v,ii)
end do
end do
end do
end if
term*=2.D0
hessmat_iatb=term
end function hessmat_iatb
real*8 function hessmat_taub(t,a,u,b)
BEGIN_DOC
! the orbital hessian for act->virt,act->virt
END_DOC
implicit none
integer :: t,a,u,b,tt,aa,uu,bb,v,vv,x,xx,y
integer :: v3,x3
real*8 :: term,t1,t2,t3
tt=list_act(t)
aa=list_virt(a)
if (t == u) then
if (a == b) then
! ta/ta
t1=occnum(tt)*Fipq(aa,aa)
t2=0.D0
t3=0.D0
t1-=occnum(tt)*Fipq(tt,tt)
do v=1,n_act_orb
vv=list_act(v)
v3=v+n_core_inact_orb
do x=1,n_act_orb
xx=list_act(x)
x3=x+n_core_inact_orb
t2+=2.D0*(P0tuvx_no(t,t,v,x)*bielec_pqxx_no(aa,aa,v3,x3) &
+(P0tuvx_no(t,x,v,t)+P0tuvx_no(t,x,t,v))* &
bielec_pxxq_no(aa,x3,v3,aa))
do y=1,n_act_orb
t3-=2.D0*P0tuvx_no(t,v,x,y)*bielecCI_no(t,v,y,xx)
end do
end do
end do
term=t1+t2+t3
else
bb=list_virt(b)
! ta/tb b/=a
term=occnum(tt)*Fipq(aa,bb)
do v=1,n_act_orb
vv=list_act(v)
v3=v+n_core_inact_orb
do x=1,n_act_orb
xx=list_act(x)
x3=x+n_core_inact_orb
term+=2.D0*(P0tuvx_no(t,t,v,x)*bielec_pqxx_no(aa,bb,v3,x3) &
+(P0tuvx_no(t,x,v,t)+P0tuvx_no(t,x,t,v)) &
*bielec_pxxq_no(aa,x3,v3,bb))
end do
end do
end if
else
! ta/ub t/=u
uu=list_act(u)
bb=list_virt(b)
term=0.D0
do v=1,n_act_orb
vv=list_act(v)
v3=v+n_core_inact_orb
do x=1,n_act_orb
xx=list_act(x)
x3=x+n_core_inact_orb
term+=2.D0*(P0tuvx_no(t,u,v,x)*bielec_pqxx_no(aa,bb,v3,x3) &
+(P0tuvx_no(t,x,v,u)+P0tuvx_no(t,x,u,v)) &
*bielec_pxxq_no(aa,x3,v3,bb))
end do
end do
if (a.eq.b) then
term-=0.5D0*(occnum(tt)*Fipq(uu,tt)+occnum(uu)*Fipq(tt,uu))
do v=1,n_act_orb
do y=1,n_act_orb
do x=1,n_act_orb
term-=P0tuvx_no(t,v,x,y)*bielecCI_no(x,y,v,uu)
term-=P0tuvx_no(u,v,x,y)*bielecCI_no(x,y,v,tt)
end do
end do
end do
end if
end if
term*=2.D0
hessmat_taub=term
end function hessmat_taub
BEGIN_PROVIDER [real*8, hessdiag, (nMonoEx)]
BEGIN_DOC
! the diagonal of the Hessian, needed for the Davidson procedure
END_DOC
implicit none
integer :: i,t,a,indx,indx_shift
real*8 :: hessmat_itju,hessmat_iajb,hessmat_taub
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP SHARED(hessdiag,n_core_inact_orb,n_act_orb,n_virt_orb,nMonoEx) &
!$OMP PRIVATE(i,indx,t,a,indx_shift)
!$OMP DO
do i=1,n_core_inact_orb
do t=1,n_act_orb
indx = t + (i-1)*n_act_orb
hessdiag(indx)=hessmat_itju(i,t,i,t)
end do
end do
!$OMP END DO NOWAIT
indx_shift = n_core_inact_orb*n_act_orb
!$OMP DO
do a=1,n_virt_orb
do i=1,n_core_inact_orb
indx = a + (i-1)*n_virt_orb + indx_shift
hessdiag(indx)=hessmat_iajb(i,a,i,a)
end do
end do
!$OMP END DO NOWAIT
indx_shift += n_core_inact_orb*n_virt_orb
!$OMP DO
do a=1,n_virt_orb
do t=1,n_act_orb
indx = a + (t-1)*n_virt_orb + indx_shift
hessdiag(indx)=hessmat_taub(t,a,t,a)
end do
end do
!$OMP END DO
!$OMP END PARALLEL
END_PROVIDER
BEGIN_PROVIDER [double precision, hessmat, (nMonoEx,nMonoEx)]
implicit none
integer :: i,j,t,u,a,b
integer :: indx,indx_tmp, jndx, jndx_tmp
integer :: ustart,bstart
real*8 :: hessmat_itju
real*8 :: hessmat_itja
real*8 :: hessmat_itua
real*8 :: hessmat_iajb
real*8 :: hessmat_iatb
real*8 :: hessmat_taub
! c-a c-v a-v
! c-a | X X X
! c-v | X X
! a-v | X
provide mo_two_e_integrals_in_map
hessmat = 0.d0
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP SHARED(hessmat,n_c_a_prov,list_idx_c_a,n_core_inact_orb,n_act_orb,mat_idx_c_a) &
!$OMP PRIVATE(indx_tmp,indx,i,t,j,u,ustart,jndx)
!$OMP DO
!!!! < Core-active| H |Core-active >
! Core-active excitations
do indx_tmp = 1, n_c_a_prov
indx = list_idx_c_a(1,indx_tmp)
i = list_idx_c_a(2,indx_tmp)
t = list_idx_c_a(3,indx_tmp)
! Core-active excitations
do j = 1, n_core_inact_orb
if (i.eq.j) then
ustart=t
else
ustart=1
end if
do u=ustart,n_act_orb
jndx = mat_idx_c_a(j,u)
hessmat(jndx,indx) = hessmat_itju(i,t,j,u)
hessmat(indx,jndx) = hessmat(jndx,indx)
enddo
enddo
enddo
!$OMP END DO NOWAIT
!$OMP END PARALLEL
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP SHARED(hessmat,n_c_a_prov,n_c_v_prov,list_idx_c_a,list_idx_c_v) &
!$OMP PRIVATE(indx_tmp,jndx_tmp,indx,i,t,j,a,jndx)
!$OMP DO
!!!! < Core-active| H |Core-VIRTUAL >
! Core-active excitations
do indx_tmp = 1, n_c_a_prov
indx = list_idx_c_a(1,indx_tmp)
i = list_idx_c_a(2,indx_tmp)
t = list_idx_c_a(3,indx_tmp)
! Core-VIRTUAL excitations
do jndx_tmp = 1, n_c_v_prov
jndx = list_idx_c_v(1,jndx_tmp)
j = list_idx_c_v(2,jndx_tmp)
a = list_idx_c_v(3,jndx_tmp)
hessmat(jndx,indx) = hessmat_itja(i,t,j,a)
hessmat(indx,jndx) = hessmat(jndx,indx)
enddo
enddo
!$OMP END DO NOWAIT
!$OMP END PARALLEL
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP SHARED(hessmat,n_c_a_prov,n_a_v_prov,list_idx_c_a,list_idx_a_v) &
!$OMP PRIVATE(indx_tmp,jndx_tmp,indx,i,t,u,a,jndx)
!$OMP DO
!!!! < Core-active| H |ACTIVE-VIRTUAL >
! Core-active excitations
do indx_tmp = 1, n_c_a_prov
indx = list_idx_c_a(1,indx_tmp)
i = list_idx_c_a(2,indx_tmp)
t = list_idx_c_a(3,indx_tmp)
! ACTIVE-VIRTUAL excitations
do jndx_tmp = 1, n_a_v_prov
jndx = list_idx_a_v(1,jndx_tmp)
u = list_idx_a_v(2,jndx_tmp)
a = list_idx_a_v(3,jndx_tmp)
hessmat(jndx,indx) = hessmat_itua(i,t,u,a)
hessmat(indx,jndx) = hessmat(jndx,indx)
enddo
enddo
!$OMP END DO NOWAIT
!$OMP END PARALLEL
if(hess_cv_cv)then
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP SHARED(hessmat,n_c_v_prov,list_idx_c_v,n_core_inact_orb,n_virt_orb,mat_idx_c_v) &
!$OMP PRIVATE(indx_tmp,indx,i,a,j,b,bstart,jndx)
!$OMP DO
!!!!! < Core-VIRTUAL | H |Core-VIRTUAL >
! Core-VIRTUAL excitations
do indx_tmp = 1, n_c_v_prov
indx = list_idx_c_v(1,indx_tmp)
i = list_idx_c_v(2,indx_tmp)
a = list_idx_c_v(3,indx_tmp)
! Core-VIRTUAL excitations
do j = 1, n_core_inact_orb
if (i.eq.j) then
bstart=a
else
bstart=1
end if
do b=bstart,n_virt_orb
jndx = mat_idx_c_v(j,b)
hessmat(jndx,indx) = hessmat_iajb(i,a,j,b)
hessmat(indx,jndx) = hessmat(jndx,indx)
enddo
enddo
enddo
!$OMP END DO NOWAIT
!$OMP END PARALLEL
endif
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP SHARED(hessmat,n_c_v_prov,n_a_v_prov,list_idx_c_v,list_idx_a_v) &
!$OMP PRIVATE(indx_tmp,jndx_tmp,indx,i,a,t,b,jndx)
!$OMP DO
!!!! < Core-VIRTUAL | H |Active-VIRTUAL >
! Core-VIRTUAL excitations
do indx_tmp = 1, n_c_v_prov
indx = list_idx_c_v(1,indx_tmp)
i = list_idx_c_v(2,indx_tmp)
a = list_idx_c_v(3,indx_tmp)
! Active-VIRTUAL excitations
do jndx_tmp = 1, n_a_v_prov
jndx = list_idx_a_v(1,jndx_tmp)
t = list_idx_a_v(2,jndx_tmp)
b = list_idx_a_v(3,jndx_tmp)
hessmat(jndx,indx) = hessmat_iatb(i,a,t,b)
hessmat(indx,jndx) = hessmat(jndx,indx)
enddo
enddo
!$OMP END DO NOWAIT
!$OMP END PARALLEL
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP SHARED(hessmat,n_a_v_prov,list_idx_a_v,n_act_orb,n_virt_orb,mat_idx_a_v) &
!$OMP PRIVATE(indx_tmp,indx,t,a,u,b,bstart,jndx)
!$OMP DO
!!!! < Active-VIRTUAL | H |Active-VIRTUAL >
! Active-VIRTUAL excitations
do indx_tmp = 1, n_a_v_prov
indx = list_idx_a_v(1,indx_tmp)
t = list_idx_a_v(2,indx_tmp)
a = list_idx_a_v(3,indx_tmp)
! Active-VIRTUAL excitations
do u=t,n_act_orb
if (t.eq.u) then
bstart=a
else
bstart=1
end if
do b=bstart,n_virt_orb
jndx = mat_idx_a_v(u,b)
hessmat(jndx,indx) = hessmat_taub(t,a,u,b)
hessmat(indx,jndx) = hessmat(jndx,indx)
enddo
enddo
enddo
!$OMP END DO NOWAIT
!$OMP END PARALLEL
END_PROVIDER

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use bitmasks
BEGIN_PROVIDER [real*8, hessmat_old, (nMonoEx,nMonoEx)]
BEGIN_DOC
! calculate the orbital hessian 2 <Psi| E_pq H E_rs |Psi>
! + <Psi| E_pq E_rs H |Psi> + <Psi| E_rs E_pq H |Psi> by hand,
! determinant per determinant, as for the gradient
!
! we assume that we have natural active orbitals
END_DOC
implicit none
integer :: indx,ihole,ipart
integer :: jndx,jhole,jpart
character*3 :: iexc,jexc
real*8 :: res
if (bavard) then
write(6,*) ' providing Hessian matrix hessmat_old '
write(6,*) ' nMonoEx = ',nMonoEx
endif
do indx=1,nMonoEx
do jndx=1,nMonoEx
hessmat_old(indx,jndx)=0.D0
end do
end do
do indx=1,nMonoEx
ihole=excit(1,indx)
ipart=excit(2,indx)
iexc=excit_class(indx)
do jndx=indx,nMonoEx
jhole=excit(1,jndx)
jpart=excit(2,jndx)
jexc=excit_class(jndx)
call calc_hess_elem(ihole,ipart,jhole,jpart,res)
hessmat_old(indx,jndx)=res
hessmat_old(jndx,indx)=res
end do
end do
END_PROVIDER
subroutine calc_hess_elem(ihole,ipart,jhole,jpart,res)
BEGIN_DOC
! eq 19 of Siegbahn et al, Physica Scripta 1980
! we calculate 2 <Psi| E_pq H E_rs |Psi>
! + <Psi| E_pq E_rs H |Psi> + <Psi| E_rs E_pq H |Psi>
! average over all states is performed.
! no transition between states.
END_DOC
implicit none
integer :: ihole,ipart,ispin,mu,istate
integer :: jhole,jpart,jspin
integer :: mu_pq, mu_pqrs, mu_rs, mu_rspq, nu_rs,nu
real*8 :: res
integer(bit_kind), allocatable :: det_mu(:,:)
integer(bit_kind), allocatable :: det_nu(:,:)
integer(bit_kind), allocatable :: det_mu_pq(:,:)
integer(bit_kind), allocatable :: det_mu_rs(:,:)
integer(bit_kind), allocatable :: det_nu_rs(:,:)
integer(bit_kind), allocatable :: det_mu_pqrs(:,:)
integer(bit_kind), allocatable :: det_mu_rspq(:,:)
real*8 :: i_H_psi_array(N_states),phase,phase2,phase3
real*8 :: i_H_j_element
allocate(det_mu(N_int,2))
allocate(det_nu(N_int,2))
allocate(det_mu_pq(N_int,2))
allocate(det_mu_rs(N_int,2))
allocate(det_nu_rs(N_int,2))
allocate(det_mu_pqrs(N_int,2))
allocate(det_mu_rspq(N_int,2))
integer :: mu_pq_possible
integer :: mu_rs_possible
integer :: nu_rs_possible
integer :: mu_pqrs_possible
integer :: mu_rspq_possible
res=0.D0
! the terms <0|E E H |0>
do mu=1,n_det
! get the string of the determinant
call det_extract(det_mu,mu,N_int)
do ispin=1,2
! do the monoexcitation pq on it
call det_copy(det_mu,det_mu_pq,N_int)
call do_signed_mono_excitation(det_mu,det_mu_pq,mu_pq &
,ihole,ipart,ispin,phase,mu_pq_possible)
if (mu_pq_possible.eq.1) then
! possible, but not necessarily in the list
! do the second excitation
do jspin=1,2
call det_copy(det_mu_pq,det_mu_pqrs,N_int)
call do_signed_mono_excitation(det_mu_pq,det_mu_pqrs,mu_pqrs&
,jhole,jpart,jspin,phase2,mu_pqrs_possible)
! excitation possible
if (mu_pqrs_possible.eq.1) then
call i_H_psi(det_mu_pqrs,psi_det,psi_coef,N_int &
,N_det,N_det,N_states,i_H_psi_array)
do istate=1,N_states
res+=i_H_psi_array(istate)*psi_coef(mu,istate)*phase*phase2
end do
end if
! try the de-excitation with opposite sign
call det_copy(det_mu_pq,det_mu_pqrs,N_int)
call do_signed_mono_excitation(det_mu_pq,det_mu_pqrs,mu_pqrs&
,jpart,jhole,jspin,phase2,mu_pqrs_possible)
phase2=-phase2
! excitation possible
if (mu_pqrs_possible.eq.1) then
call i_H_psi(det_mu_pqrs,psi_det,psi_coef,N_int &
,N_det,N_det,N_states,i_H_psi_array)
do istate=1,N_states
res+=i_H_psi_array(istate)*psi_coef(mu,istate)*phase*phase2
end do
end if
end do
end if
! exchange the notion of pq and rs
! do the monoexcitation rs on the initial determinant
call det_copy(det_mu,det_mu_rs,N_int)
call do_signed_mono_excitation(det_mu,det_mu_rs,mu_rs &
,jhole,jpart,ispin,phase2,mu_rs_possible)
if (mu_rs_possible.eq.1) then
! do the second excitation
do jspin=1,2
call det_copy(det_mu_rs,det_mu_rspq,N_int)
call do_signed_mono_excitation(det_mu_rs,det_mu_rspq,mu_rspq&
,ihole,ipart,jspin,phase3,mu_rspq_possible)
! excitation possible (of course, the result is outside the CAS)
if (mu_rspq_possible.eq.1) then
call i_H_psi(det_mu_rspq,psi_det,psi_coef,N_int &
,N_det,N_det,N_states,i_H_psi_array)
do istate=1,N_states
res+=i_H_psi_array(istate)*psi_coef(mu,istate)*phase2*phase3
end do
end if
! we may try the de-excitation, with opposite sign
call det_copy(det_mu_rs,det_mu_rspq,N_int)
call do_signed_mono_excitation(det_mu_rs,det_mu_rspq,mu_rspq&
,ipart,ihole,jspin,phase3,mu_rspq_possible)
phase3=-phase3
! excitation possible (of course, the result is outside the CAS)
if (mu_rspq_possible.eq.1) then
call i_H_psi(det_mu_rspq,psi_det,psi_coef,N_int &
,N_det,N_det,N_states,i_H_psi_array)
do istate=1,N_states
res+=i_H_psi_array(istate)*psi_coef(mu,istate)*phase2*phase3
end do
end if
end do
end if
!
! the operator E H E, we have to do a double loop over the determinants
! we still have the determinant mu_pq and the phase in memory
if (mu_pq_possible.eq.1) then
do nu=1,N_det
call det_extract(det_nu,nu,N_int)
do jspin=1,2
call det_copy(det_nu,det_nu_rs,N_int)
call do_signed_mono_excitation(det_nu,det_nu_rs,nu_rs &
,jhole,jpart,jspin,phase2,nu_rs_possible)
! excitation possible ?
if (nu_rs_possible.eq.1) then
call i_H_j(det_mu_pq,det_nu_rs,N_int,i_H_j_element)
do istate=1,N_states
res+=2.D0*i_H_j_element*psi_coef(mu,istate) &
*psi_coef(nu,istate)*phase*phase2
end do
end if
end do
end do
end if
end do
end do
! state-averaged Hessian
res*=1.D0/dble(N_states)
end subroutine calc_hess_elem
BEGIN_PROVIDER [real*8, hessmat_peter, (nMonoEx,nMonoEx)]
BEGIN_DOC
! explicit hessian matrix from density matrices and integrals
! of course, this will be used for a direct Davidson procedure later
! we will not store the matrix in real life
! formulas are broken down as functions for the 6 classes of matrix elements
!
END_DOC
implicit none
integer :: i,j,t,u,a,b,indx,jndx,bstart,ustart,indx_shift
real*8 :: hessmat_itju
real*8 :: hessmat_itja
real*8 :: hessmat_itua
real*8 :: hessmat_iajb
real*8 :: hessmat_iatb
real*8 :: hessmat_taub
if (bavard) then
write(6,*) ' providing Hessian matrix hessmat_peter '
write(6,*) ' nMonoEx = ',nMonoEx
endif
provide mo_two_e_integrals_in_map
!$OMP PARALLEL DEFAULT(NONE) &
!$OMP SHARED(hessmat_peter,n_core_inact_orb,n_act_orb,n_virt_orb,nMonoEx) &
!$OMP PRIVATE(i,indx,jndx,j,ustart,t,u,a,bstart,indx_shift)
!$OMP DO
! (DOUBLY OCCUPIED ---> ACT )
do i=1,n_core_inact_orb
do t=1,n_act_orb
indx = t + (i-1)*n_act_orb
jndx=indx
! (DOUBLY OCCUPIED ---> ACT )
do j=i,n_core_inact_orb
if (i.eq.j) then
ustart=t
else
ustart=1
end if
do u=ustart,n_act_orb
hessmat_peter(jndx,indx)=hessmat_itju(i,t,j,u)
jndx+=1
end do
end do
! (DOUBLY OCCUPIED ---> VIRTUAL)
do j=1,n_core_inact_orb
do a=1,n_virt_orb
hessmat_peter(jndx,indx)=hessmat_itja(i,t,j,a)
jndx+=1
end do
end do
! (ACTIVE ---> VIRTUAL)
do u=1,n_act_orb
do a=1,n_virt_orb
hessmat_peter(jndx,indx)=hessmat_itua(i,t,u,a)
jndx+=1
end do
end do
end do
end do
!$OMP END DO NOWAIT
indx_shift = n_core_inact_orb*n_act_orb
!$OMP DO
! (DOUBLY OCCUPIED ---> VIRTUAL)
do a=1,n_virt_orb
do i=1,n_core_inact_orb
indx = a + (i-1)*n_virt_orb + indx_shift
jndx=indx
! (DOUBLY OCCUPIED ---> VIRTUAL)
do j=i,n_core_inact_orb
if (i.eq.j) then
bstart=a
else
bstart=1
end if
do b=bstart,n_virt_orb
hessmat_peter(jndx,indx)=hessmat_iajb(i,a,j,b)
jndx+=1
end do
end do
! (ACT ---> VIRTUAL)
do t=1,n_act_orb
do b=1,n_virt_orb
hessmat_peter(jndx,indx)=hessmat_iatb(i,a,t,b)
jndx+=1
end do
end do
end do
end do
!$OMP END DO NOWAIT
indx_shift += n_core_inact_orb*n_virt_orb
!$OMP DO
! (ACT ---> VIRTUAL)
do a=1,n_virt_orb
do t=1,n_act_orb
indx = a + (t-1)*n_virt_orb + indx_shift
jndx=indx
! (ACT ---> VIRTUAL)
do u=t,n_act_orb
if (t.eq.u) then
bstart=a
else
bstart=1
end if
do b=bstart,n_virt_orb
hessmat_peter(jndx,indx)=hessmat_taub(t,a,u,b)
jndx+=1
end do
end do
end do
end do
!$OMP END DO
!$OMP END PARALLEL
do jndx=1,nMonoEx
do indx=1,jndx-1
hessmat_peter(indx,jndx) = hessmat_peter(jndx,indx)
enddo
enddo
END_PROVIDER

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BEGIN_PROVIDER [real*8, Fipq, (mo_num,mo_num) ]
BEGIN_DOC
! the inactive Fock matrix, in molecular orbitals
END_DOC
implicit none
integer :: p,q,k,kk,t,tt,u,uu
do q=1,mo_num
do p=1,mo_num
Fipq(p,q)=one_ints_no(p,q)
end do
end do
! the inactive Fock matrix
do k=1,n_core_inact_orb
kk=list_core_inact(k)
do q=1,mo_num
do p=1,mo_num
Fipq(p,q)+=2.D0*bielec_pqxx_no(p,q,k,k) -bielec_pxxq_no(p,k,k,q)
end do
end do
end do
if (bavard) then
integer :: i
write(6,*)
write(6,*) ' the diagonal of the inactive effective Fock matrix '
write(6,'(5(i3,F12.5))') (i,Fipq(i,i),i=1,mo_num)
write(6,*)
end if
END_PROVIDER
BEGIN_PROVIDER [real*8, Fapq, (mo_num,mo_num) ]
BEGIN_DOC
! the active active Fock matrix, in molecular orbitals
! we create them in MOs, quite expensive
!
! for an implementation in AOs we need first the natural orbitals
! for forming an active density matrix in AOs
!
END_DOC
implicit none
integer :: p,q,k,kk,t,tt,u,uu
Fapq = 0.d0
! the active Fock matrix, D0tu is diagonal
do t=1,n_act_orb
tt=list_act(t)
do q=1,mo_num
do p=1,mo_num
Fapq(p,q)+=occnum(tt) &
*(bielec_pqxx_no(p,q,tt,tt)-0.5D0*bielec_pxxq_no(p,tt,tt,q))
end do
end do
end do
if (bavard) then
integer :: i
write(6,*)
write(6,*) ' the effective Fock matrix over MOs'
write(6,*)
write(6,*)
write(6,*) ' the diagonal of the inactive effective Fock matrix '
write(6,'(5(i3,F12.5))') (i,Fipq(i,i),i=1,mo_num)
write(6,*)
write(6,*)
write(6,*) ' the diagonal of the active Fock matrix '
write(6,'(5(i3,F12.5))') (i,Fapq(i,i),i=1,mo_num)
write(6,*)
end if
END_PROVIDER

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BEGIN_PROVIDER [real*8, occnum, (mo_num)]
implicit none
BEGIN_DOC
! MO occupation numbers
END_DOC
integer :: i
occnum=0.D0
do i=1,n_core_inact_orb
occnum(list_core_inact(i))=2.D0
end do
do i=1,n_act_orb
occnum(list_act(i))=occ_act(i)
end do
if (bavard) then
write(6,*) ' occupation numbers '
do i=1,mo_num
write(6,*) i,occnum(i)
end do
endif
END_PROVIDER
BEGIN_PROVIDER [ real*8, natorbsCI, (n_act_orb,n_act_orb) ]
&BEGIN_PROVIDER [ real*8, occ_act, (n_act_orb) ]
implicit none
BEGIN_DOC
! Natural orbitals of CI
END_DOC
integer :: i, j
double precision :: Vt(n_act_orb,n_act_orb)
! call lapack_diag(occ_act,natorbsCI,D0tu,n_act_orb,n_act_orb)
call svd(D0tu, size(D0tu,1), natorbsCI,size(natorbsCI,1), occ_act, Vt, size(Vt,1),n_act_orb,n_act_orb)
if (bavard) then
write(6,*) ' found occupation numbers as '
do i=1,n_act_orb
write(6,*) i,occ_act(i)
end do
integer :: nmx
real*8 :: xmx
do i=1,n_act_orb
! largest element of the eigenvector should be positive
xmx=0.D0
nmx=0
do j=1,n_act_orb
if (abs(natOrbsCI(j,i)).gt.xmx) then
nmx=j
xmx=abs(natOrbsCI(j,i))
end if
end do
xmx=sign(1.D0,natOrbsCI(nmx,i))
do j=1,n_act_orb
natOrbsCI(j,i)*=xmx
end do
write(6,*) ' Eigenvector No ',i
write(6,'(5(I3,F12.5))') (j,natOrbsCI(j,i),j=1,n_act_orb)
end do
end if
END_PROVIDER
BEGIN_PROVIDER [real*8, P0tuvx_no, (n_act_orb,n_act_orb,n_act_orb,n_act_orb)]
implicit none
BEGIN_DOC
! 4-index transformation of 2part matrices
END_DOC
integer :: i,j,k,l,p,q
real*8 :: d(n_act_orb)
! index per index
! first quarter
P0tuvx_no(:,:,:,:) = P0tuvx(:,:,:,:)
do j=1,n_act_orb
do k=1,n_act_orb
do l=1,n_act_orb
do p=1,n_act_orb
d(p)=0.D0
end do
do p=1,n_act_orb
do q=1,n_act_orb
d(p)+=P0tuvx_no(q,j,k,l)*natorbsCI(q,p)
end do
end do
do p=1,n_act_orb
P0tuvx_no(p,j,k,l)=d(p)
end do
end do
end do
end do
! 2nd quarter
do j=1,n_act_orb
do k=1,n_act_orb
do l=1,n_act_orb
do p=1,n_act_orb
d(p)=0.D0
end do
do p=1,n_act_orb
do q=1,n_act_orb
d(p)+=P0tuvx_no(j,q,k,l)*natorbsCI(q,p)
end do
end do
do p=1,n_act_orb
P0tuvx_no(j,p,k,l)=d(p)
end do
end do
end do
end do
! 3rd quarter
do j=1,n_act_orb
do k=1,n_act_orb
do l=1,n_act_orb
do p=1,n_act_orb
d(p)=0.D0
end do
do p=1,n_act_orb
do q=1,n_act_orb
d(p)+=P0tuvx_no(j,k,q,l)*natorbsCI(q,p)
end do
end do
do p=1,n_act_orb
P0tuvx_no(j,k,p,l)=d(p)
end do
end do
end do
end do
! 4th quarter
do j=1,n_act_orb
do k=1,n_act_orb
do l=1,n_act_orb
do p=1,n_act_orb
d(p)=0.D0
end do
do p=1,n_act_orb
do q=1,n_act_orb
d(p)+=P0tuvx_no(j,k,l,q)*natorbsCI(q,p)
end do
end do
do p=1,n_act_orb
P0tuvx_no(j,k,l,p)=d(p)
end do
end do
end do
end do
END_PROVIDER
BEGIN_PROVIDER [real*8, one_ints_no, (mo_num,mo_num)]
implicit none
BEGIN_DOC
! Transformed one-e integrals
END_DOC
integer :: i,j, p, q
real*8 :: d(n_act_orb)
one_ints_no(:,:)=mo_one_e_integrals(:,:)
! 1st half-trf
do j=1,mo_num
do p=1,n_act_orb
d(p)=0.D0
end do
do p=1,n_act_orb
do q=1,n_act_orb
d(p)+=one_ints_no(list_act(q),j)*natorbsCI(q,p)
end do
end do
do p=1,n_act_orb
one_ints_no(list_act(p),j)=d(p)
end do
end do
! 2nd half-trf
do j=1,mo_num
do p=1,n_act_orb
d(p)=0.D0
end do
do p=1,n_act_orb
do q=1,n_act_orb
d(p)+=one_ints_no(j,list_act(q))*natorbsCI(q,p)
end do
end do
do p=1,n_act_orb
one_ints_no(j,list_act(p))=d(p)
end do
end do
END_PROVIDER
BEGIN_PROVIDER [ double precision, NatOrbsCI_mos, (mo_num, mo_num) ]
implicit none
BEGIN_DOC
! Rotation matrix from current MOs to the CI natural MOs
END_DOC
integer :: p,q
NatOrbsCI_mos(:,:) = 0.d0
do q = 1,mo_num
NatOrbsCI_mos(q,q) = 1.d0
enddo
do q = 1,n_act_orb
do p = 1,n_act_orb
NatOrbsCI_mos(list_act(p),list_act(q)) = natorbsCI(p,q)
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [real*8, NatOrbsFCI, (ao_num,mo_num)]
implicit none
BEGIN_DOC
! FCI natural orbitals
END_DOC
call dgemm('N','N', ao_num,mo_num,mo_num,1.d0, &
mo_coef, size(mo_coef,1), &
NatOrbsCI_mos, size(NatOrbsCI_mos,1), 0.d0, &
NatOrbsFCI, size(NatOrbsFCI,1))
END_PROVIDER

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BEGIN_PROVIDER [real*8, SXmatrix, (nMonoEx+1,nMonoEx+1)]
&BEGIN_PROVIDER [integer, n_guess_sx_mat ]
implicit none
BEGIN_DOC
! Single-excitation matrix
END_DOC
integer :: i,j
do i=1,nMonoEx+1
do j=1,nMonoEx+1
SXmatrix(i,j)=0.D0
end do
end do
do i=1,nMonoEx
SXmatrix(1,i+1)=gradvec2(i)
SXmatrix(1+i,1)=gradvec2(i)
end do
if(diag_hess_cas)then
do i = 1, nMonoEx
SXmatrix(i+1,i+1) = hessdiag(i)
enddo
else
do i=1,nMonoEx
do j=1,nMonoEx
SXmatrix(i+1,j+1)=hessmat(i,j)
SXmatrix(j+1,i+1)=hessmat(i,j)
end do
end do
endif
do i = 1, nMonoEx
SXmatrix(i+1,i+1) += level_shift_casscf
enddo
n_guess_sx_mat = 1
do i = 1, nMonoEx
if(SXmatrix(i+1,i+1).lt.0.d0 )then
n_guess_sx_mat += 1
endif
enddo
if (bavard) then
do i=2,nMonoEx
write(6,*) ' diagonal of the Hessian : ',i,hessmat(i,i)
end do
end if
END_PROVIDER
BEGIN_PROVIDER [real*8, SXeigenvec, (nMonoEx+1,nMonoEx+1)]
&BEGIN_PROVIDER [real*8, SXeigenval, (nMonoEx+1)]
implicit none
BEGIN_DOC
! Eigenvectors/eigenvalues of the single-excitation matrix
END_DOC
if(nMonoEx+1.gt.n_det_max_full)then
if(bavard)then
print*,'Using the Davidson algorithm to diagonalize the SXmatrix'
endif
double precision, allocatable :: u_in(:,:),energies(:)
allocate(u_in(nMonoEx+1,n_states_diag),energies(n_guess_sx_mat))
call davidson_diag_sx_mat(n_guess_sx_mat, u_in, energies)
integer :: i,j
SXeigenvec = 0.d0
SXeigenval = 0.d0
do i = 1, n_guess_sx_mat
SXeigenval(i) = energies(i)
do j = 1, nMonoEx+1
SXeigenvec(j,i) = u_in(j,i)
enddo
enddo
else
if(bavard)then
print*,'Diagonalize the SXmatrix with Jacobi'
endif
call lapack_diag(SXeigenval,SXeigenvec,SXmatrix,nMonoEx+1,nMonoEx+1)
endif
if (bavard) then
write(6,*) ' SXdiag : lowest eigenvalues '
write(6,*) ' 1 - ',SXeigenval(1),SXeigenvec(1,1)
if(n_guess_sx_mat.gt.0)then
write(6,*) ' 2 - ',SXeigenval(2),SXeigenvec(1,2)
write(6,*) ' 3 - ',SXeigenval(3),SXeigenvec(1,3)
write(6,*) ' 4 - ',SXeigenval(4),SXeigenvec(1,4)
write(6,*) ' 5 - ',SXeigenval(5),SXeigenvec(1,5)
endif
write(6,*)
write(6,*) ' SXdiag : lowest eigenvalue = ',SXeigenval(1)
endif
END_PROVIDER
BEGIN_PROVIDER [real*8, energy_improvement]
implicit none
if(state_following_casscf)then
energy_improvement = SXeigenval(best_vector_ovrlp_casscf)
else
energy_improvement = SXeigenval(1)
endif
END_PROVIDER
BEGIN_PROVIDER [ integer, best_vector_ovrlp_casscf ]
&BEGIN_PROVIDER [ double precision, best_overlap_casscf ]
implicit none
integer :: i
double precision :: c0
best_overlap_casscf = 0.D0
best_vector_ovrlp_casscf = -1000
do i=1,nMonoEx+1
if (SXeigenval(i).lt.0.D0) then
if (dabs(SXeigenvec(1,i)).gt.best_overlap_casscf) then
best_overlap_casscf=dabs(SXeigenvec(1,i))
best_vector_ovrlp_casscf = i
end if
end if
end do
if(best_vector_ovrlp_casscf.lt.0)then
best_vector_ovrlp_casscf = minloc(SXeigenval,nMonoEx+1)
endif
c0=SXeigenvec(1,best_vector_ovrlp_casscf)
if (bavard) then
write(6,*) ' SXdiag : eigenvalue for best overlap with '
write(6,*) ' previous orbitals = ',SXeigenval(best_vector_ovrlp_casscf)
write(6,*) ' weight of the 1st element ',c0
endif
END_PROVIDER
BEGIN_PROVIDER [double precision, SXvector, (nMonoEx+1)]
implicit none
BEGIN_DOC
! Best eigenvector of the single-excitation matrix
END_DOC
integer :: i
double precision :: c0
c0=SXeigenvec(1,best_vector_ovrlp_casscf)
do i=1,nMonoEx+1
SXvector(i)=SXeigenvec(i,best_vector_ovrlp_casscf)/c0
end do
END_PROVIDER
BEGIN_PROVIDER [double precision, NewOrbs, (ao_num,mo_num) ]
implicit none
BEGIN_DOC
! Updated orbitals
END_DOC
integer :: i,j,ialph
if(state_following_casscf)then
print*,'Using the state following casscf '
call dgemm('N','T', ao_num,mo_num,mo_num,1.d0, &
NatOrbsFCI, size(NatOrbsFCI,1), &
Umat, size(Umat,1), 0.d0, &
NewOrbs, size(NewOrbs,1))
level_shift_casscf *= 0.5D0
level_shift_casscf = max(level_shift_casscf,0.002d0)
!touch level_shift_casscf
else
if(best_vector_ovrlp_casscf.ne.1.and.n_orb_swap.ne.0)then
print*,'Taking the lowest root for the CASSCF'
print*,'!!! SWAPPING MOS !!!!!!'
level_shift_casscf *= 2.D0
level_shift_casscf = min(level_shift_casscf,0.5d0)
print*,'level_shift_casscf = ',level_shift_casscf
NewOrbs = switch_mo_coef
!mo_coef = switch_mo_coef
!soft_touch mo_coef
!call save_mos_no_occ
!stop
else
level_shift_casscf *= 0.5D0
level_shift_casscf = max(level_shift_casscf,0.002d0)
!touch level_shift_casscf
call dgemm('N','T', ao_num,mo_num,mo_num,1.d0, &
NatOrbsFCI, size(NatOrbsFCI,1), &
Umat, size(Umat,1), 0.d0, &
NewOrbs, size(NewOrbs,1))
endif
endif
END_PROVIDER
BEGIN_PROVIDER [real*8, Umat, (mo_num,mo_num) ]
implicit none
BEGIN_DOC
! Orbital rotation matrix
END_DOC
integer :: i,j,indx,k,iter,t,a,ii,tt,aa
logical :: converged
real*8 :: Tpotmat (mo_num,mo_num), Tpotmat2 (mo_num,mo_num)
real*8 :: Tmat(mo_num,mo_num)
real*8 :: f
! the orbital rotation matrix T
Tmat(:,:)=0.D0
indx=1
do i=1,n_core_inact_orb
ii=list_core_inact(i)
do t=1,n_act_orb
tt=list_act(t)
indx+=1
Tmat(ii,tt)= SXvector(indx)
Tmat(tt,ii)=-SXvector(indx)
end do
end do
do i=1,n_core_inact_orb
ii=list_core_inact(i)
do a=1,n_virt_orb
aa=list_virt(a)
indx+=1
Tmat(ii,aa)= SXvector(indx)
Tmat(aa,ii)=-SXvector(indx)
end do
end do
do t=1,n_act_orb
tt=list_act(t)
do a=1,n_virt_orb
aa=list_virt(a)
indx+=1
Tmat(tt,aa)= SXvector(indx)
Tmat(aa,tt)=-SXvector(indx)
end do
end do
! Form the exponential
Tpotmat(:,:)=0.D0
Umat(:,:) =0.D0
do i=1,mo_num
Tpotmat(i,i)=1.D0
Umat(i,i) =1.d0
end do
iter=0
converged=.false.
do while (.not.converged)
iter+=1
f = 1.d0 / dble(iter)
Tpotmat2(:,:) = Tpotmat(:,:) * f
call dgemm('N','N', mo_num,mo_num,mo_num,1.d0, &
Tpotmat2, size(Tpotmat2,1), &
Tmat, size(Tmat,1), 0.d0, &
Tpotmat, size(Tpotmat,1))
Umat(:,:) = Umat(:,:) + Tpotmat(:,:)
converged = ( sum(abs(Tpotmat(:,:))) < 1.d-6).or.(iter>30)
end do
END_PROVIDER

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subroutine reorder_orbitals_for_casscf
implicit none
BEGIN_DOC
! routine that reorders the orbitals of the CASSCF in terms block of core, active and virtual
END_DOC
integer :: i,j,iorb
integer, allocatable :: iorder(:),array(:)
allocate(iorder(mo_num),array(mo_num))
do i = 1, n_core_orb
iorb = list_core(i)
array(iorb) = i
enddo
do i = 1, n_inact_orb
iorb = list_inact(i)
array(iorb) = mo_num + i
enddo
do i = 1, n_act_orb
iorb = list_act(i)
array(iorb) = 2 * mo_num + i
enddo
do i = 1, n_virt_orb
iorb = list_virt(i)
array(iorb) = 3 * mo_num + i
enddo
do i = 1, mo_num
iorder(i) = i
enddo
call isort(array,iorder,mo_num)
double precision, allocatable :: mo_coef_new(:,:)
allocate(mo_coef_new(ao_num,mo_num))
do i = 1, mo_num
mo_coef_new(:,i) = mo_coef(:,iorder(i))
enddo
mo_coef = mo_coef_new
touch mo_coef
list_core_reverse = 0
do i = 1, n_core_orb
list_core(i) = i
list_core_reverse(i) = i
mo_class(i) = "Core"
enddo
list_inact_reverse = 0
do i = 1, n_inact_orb
list_inact(i) = i + n_core_orb
list_inact_reverse(i+n_core_orb) = i
mo_class(i+n_core_orb) = "Inactive"
enddo
list_act_reverse = 0
do i = 1, n_act_orb
list_act(i) = n_core_inact_orb + i
list_act_reverse(n_core_inact_orb + i) = i
mo_class(n_core_inact_orb + i) = "Active"
enddo
list_virt_reverse = 0
do i = 1, n_virt_orb
list_virt(i) = n_core_inact_orb + n_act_orb + i
list_virt_reverse(n_core_inact_orb + n_act_orb + i) = i
mo_class(n_core_inact_orb + n_act_orb + i) = "Virtual"
enddo
touch list_core_reverse list_core list_inact list_inact_reverse list_act list_act_reverse list_virt list_virt_reverse
end

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subroutine save_energy(E,pt2)
implicit none
BEGIN_DOC
! Saves the energy in |EZFIO|.
END_DOC
double precision, intent(in) :: E(N_states), pt2(N_states)
call ezfio_set_casscf_cipsi_energy(E(1:N_states))
call ezfio_set_casscf_cipsi_energy_pt2(E(1:N_states)+pt2(1:N_states))
end

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BEGIN_PROVIDER [double precision, super_ci_dm, (mo_num,mo_num)]
implicit none
BEGIN_DOC
! density matrix of the super CI matrix, in the basis of NATURAL ORBITALS OF THE CASCI WF
!
! This is obtained from annex B of Roos et. al. Chemical Physics 48 (1980) 157-173
!
! WARNING ::: in the equation B3.d there is a TYPO with a forgotten MINUS SIGN (see variable mat_tmp_dm_super_ci )
END_DOC
super_ci_dm = 0.d0
integer :: i,j,iorb,jorb
integer :: a,aorb,b,borb
integer :: t,torb,v,vorb,u,uorb,x,xorb
double precision :: c0,ci
c0 = SXeigenvec(1,1)
! equation B3.a of the annex B of Roos et. al. Chemical Physics 48 (1980) 157-173
! loop over the core/inact
do i = 1, n_core_inact_orb
iorb = list_core_inact(i)
super_ci_dm(iorb,iorb) = 2.d0 ! first term of B3.a
! loop over the core/inact
do j = 1, n_core_inact_orb
jorb = list_core_inact(j)
! loop over the virtual
do a = 1, n_virt_orb
aorb = list_virt(a)
super_ci_dm(jorb,iorb) += -2.d0 * lowest_super_ci_coef_mo(aorb,iorb) * lowest_super_ci_coef_mo(aorb,jorb) ! second term in B3.a
enddo
do t = 1, n_act_orb
torb = list_act(t)
! thrid term of the B3.a
super_ci_dm(jorb,iorb) += - lowest_super_ci_coef_mo(iorb,torb) * lowest_super_ci_coef_mo(jorb,torb) * (2.d0 - occ_act(t))
enddo
enddo
enddo
! equation B3.b of the annex B of Roos et. al. Chemical Physics 48 (1980) 157-173
do i = 1, n_core_inact_orb
iorb = list_core_inact(i)
do t = 1, n_act_orb
torb = list_act(t)
super_ci_dm(iorb,torb) = c0 * lowest_super_ci_coef_mo(torb,iorb) * (2.d0 - occ_act(t))
super_ci_dm(torb,iorb) = c0 * lowest_super_ci_coef_mo(torb,iorb) * (2.d0 - occ_act(t))
do a = 1, n_virt_orb
aorb = list_virt(a)
super_ci_dm(iorb,torb) += - lowest_super_ci_coef_mo(aorb,iorb) * lowest_super_ci_coef_mo(aorb,torb) * occ_act(t)
super_ci_dm(torb,iorb) += - lowest_super_ci_coef_mo(aorb,iorb) * lowest_super_ci_coef_mo(aorb,torb) * occ_act(t)
enddo
enddo
enddo
! equation B3.c of the annex B of Roos et. al. Chemical Physics 48 (1980) 157-173
do i = 1, n_core_inact_orb
iorb = list_core_inact(i)
do a = 1, n_virt_orb
aorb = list_virt(a)
super_ci_dm(aorb,iorb) = 2.d0 * c0 * lowest_super_ci_coef_mo(aorb,iorb)
super_ci_dm(iorb,aorb) = 2.d0 * c0 * lowest_super_ci_coef_mo(aorb,iorb)
enddo
enddo
! equation B3.d of the annex B of Roos et. al. Chemical Physics 48 (1980) 157-173
do t = 1, n_act_orb
torb = list_act(t)
super_ci_dm(torb,torb) = occ_act(t) ! first term of equation B3.d
do x = 1, n_act_orb
xorb = list_act(x)
super_ci_dm(torb,torb) += - occ_act(x) * occ_act(t)* mat_tmp_dm_super_ci(x,x) ! second term involving the ONE-rdm
enddo
do u = 1, n_act_orb
uorb = list_act(u)
! second term of equation B3.d
do x = 1, n_act_orb
xorb = list_act(x)
do v = 1, n_act_orb
vorb = list_act(v)
super_ci_dm(torb,uorb) += 2.d0 * P0tuvx_no(v,x,t,u) * mat_tmp_dm_super_ci(v,x) ! second term involving the TWO-rdm
enddo
enddo
! third term of equation B3.d
do i = 1, n_core_inact_orb
iorb = list_core_inact(i)
super_ci_dm(torb,uorb) += lowest_super_ci_coef_mo(iorb,torb) * lowest_super_ci_coef_mo(iorb,uorb) * (2.d0 - occ_act(t) - occ_act(u))
enddo
enddo
enddo
! equation B3.e of the annex B of Roos et. al. Chemical Physics 48 (1980) 157-173
do t = 1, n_act_orb
torb = list_act(t)
do a = 1, n_virt_orb
aorb = list_virt(a)
super_ci_dm(aorb,torb) += c0 * lowest_super_ci_coef_mo(aorb,torb) * occ_act(t)
super_ci_dm(torb,aorb) += c0 * lowest_super_ci_coef_mo(aorb,torb) * occ_act(t)
do i = 1, n_core_inact_orb
iorb = list_core_inact(i)
super_ci_dm(aorb,torb) += lowest_super_ci_coef_mo(iorb,aorb) * lowest_super_ci_coef_mo(iorb,torb) * (2.d0 - occ_act(t))
super_ci_dm(torb,aorb) += lowest_super_ci_coef_mo(iorb,aorb) * lowest_super_ci_coef_mo(iorb,torb) * (2.d0 - occ_act(t))
enddo
enddo
enddo
! equation B3.f of the annex B of Roos et. al. Chemical Physics 48 (1980) 157-173
do a = 1, n_virt_orb
aorb = list_virt(a)
do b = 1, n_virt_orb
borb= list_virt(b)
! First term of equation B3.f
do i = 1, n_core_inact_orb
iorb = list_core_inact(i)
super_ci_dm(borb,aorb) += 2.d0 * lowest_super_ci_coef_mo(iorb,aorb) * lowest_super_ci_coef_mo(iorb,borb)
enddo
! Second term of equation B3.f
do t = 1, n_act_orb
torb = list_act(t)
super_ci_dm(borb,aorb) += lowest_super_ci_coef_mo(torb,aorb) * lowest_super_ci_coef_mo(torb,borb) * occ_act(t)
enddo
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [double precision, superci_natorb, (ao_num,mo_num)
&BEGIN_PROVIDER [double precision, superci_nat_occ, (mo_num)
implicit none
call general_mo_coef_new_as_svd_vectors_of_mo_matrix_eig(super_ci_dm,mo_num,mo_num,mo_num,NatOrbsFCI,superci_nat_occ,superci_natorb)
END_PROVIDER
BEGIN_PROVIDER [double precision, mat_tmp_dm_super_ci, (n_act_orb,n_act_orb)]
implicit none
BEGIN_DOC
! computation of the term in [ ] in the equation B3.d of Roos et. al. Chemical Physics 48 (1980) 157-173
!
! !!!!! WARNING !!!!!! there is a TYPO: a MINUS SIGN SHOULD APPEAR in that term
END_DOC
integer :: a,aorb,i,iorb
integer :: x,xorb,v,vorb
mat_tmp_dm_super_ci = 0.d0
do v = 1, n_act_orb
vorb = list_act(v)
do x = 1, n_act_orb
xorb = list_act(x)
do a = 1, n_virt_orb
aorb = list_virt(a)
mat_tmp_dm_super_ci(x,v) += lowest_super_ci_coef_mo(aorb,vorb) * lowest_super_ci_coef_mo(aorb,xorb)
enddo
do i = 1, n_core_inact_orb
iorb = list_core_inact(i)
! MARK THE MINUS SIGN HERE !!!!!!!!!!! BECAUSE OF TYPO IN THE ORIGINAL PAPER
mat_tmp_dm_super_ci(x,v) -= lowest_super_ci_coef_mo(iorb,vorb) * lowest_super_ci_coef_mo(iorb,xorb)
enddo
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [double precision, lowest_super_ci_coef_mo, (mo_num,mo_num)]
implicit none
integer :: i,j,iorb,jorb
integer :: a, aorb,t, torb
double precision :: sqrt2
sqrt2 = 1.d0/dsqrt(2.d0)
do i = 1, nMonoEx
iorb = excit(1,i)
jorb = excit(2,i)
lowest_super_ci_coef_mo(iorb,jorb) = SXeigenvec(i+1,1)
lowest_super_ci_coef_mo(jorb,iorb) = SXeigenvec(i+1,1)
enddo
! a_{it} of the equation B.2 of Roos et. al. Chemical Physics 48 (1980) 157-173
do i = 1, n_core_inact_orb
iorb = list_core_inact(i)
do t = 1, n_act_orb
torb = list_act(t)
lowest_super_ci_coef_mo(torb,iorb) *= (2.d0 - occ_act(t))**(-0.5d0)
lowest_super_ci_coef_mo(iorb,torb) *= (2.d0 - occ_act(t))**(-0.5d0)
enddo
enddo
! a_{ia} of the equation B.2 of Roos et. al. Chemical Physics 48 (1980) 157-173
do i = 1, n_core_inact_orb
iorb = list_core_inact(i)
do a = 1, n_virt_orb
aorb = list_virt(a)
lowest_super_ci_coef_mo(aorb,iorb) *= sqrt2
lowest_super_ci_coef_mo(iorb,aorb) *= sqrt2
enddo
enddo
! a_{ta} of the equation B.2 of Roos et. al. Chemical Physics 48 (1980) 157-173
do a = 1, n_virt_orb
aorb = list_virt(a)
do t = 1, n_act_orb
torb = list_act(t)
lowest_super_ci_coef_mo(torb,aorb) *= occ_act(t)**(-0.5d0)
lowest_super_ci_coef_mo(aorb,torb) *= occ_act(t)**(-0.5d0)
enddo
enddo
END_PROVIDER

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BEGIN_PROVIDER [double precision, SXvector_lowest, (nMonoEx)]
implicit none
integer :: i
do i=2,nMonoEx+1
SXvector_lowest(i-1)=SXeigenvec(i,1)
enddo
END_PROVIDER
BEGIN_PROVIDER [double precision, thresh_overlap_switch]
implicit none
thresh_overlap_switch = 0.5d0
END_PROVIDER
BEGIN_PROVIDER [integer, max_overlap, (nMonoEx)]
&BEGIN_PROVIDER [integer, n_max_overlap]
&BEGIN_PROVIDER [integer, dim_n_max_overlap]
implicit none
double precision, allocatable :: vec_tmp(:)
integer, allocatable :: iorder(:)
allocate(vec_tmp(nMonoEx),iorder(nMonoEx))
integer :: i
do i = 1, nMonoEx
iorder(i) = i
vec_tmp(i) = -dabs(SXvector_lowest(i))
enddo
call dsort(vec_tmp,iorder,nMonoEx)
n_max_overlap = 0
do i = 1, nMonoEx
if(dabs(vec_tmp(i)).gt.thresh_overlap_switch)then
n_max_overlap += 1
max_overlap(n_max_overlap) = iorder(i)
endif
enddo
dim_n_max_overlap = max(1,n_max_overlap)
END_PROVIDER
BEGIN_PROVIDER [integer, orb_swap, (2,dim_n_max_overlap)]
&BEGIN_PROVIDER [integer, index_orb_swap, (dim_n_max_overlap)]
&BEGIN_PROVIDER [integer, n_orb_swap ]
implicit none
use bitmasks ! you need to include the bitmasks_module.f90 features
integer :: i,imono,iorb,jorb,j
n_orb_swap = 0
do i = 1, n_max_overlap
imono = max_overlap(i)
iorb = excit(1,imono)
jorb = excit(2,imono)
if (excit_class(imono) == "c-a" .and.hessmat(imono,imono).gt.0.d0)then ! core --> active rotation
n_orb_swap += 1
orb_swap(1,n_orb_swap) = iorb ! core
orb_swap(2,n_orb_swap) = jorb ! active
index_orb_swap(n_orb_swap) = imono
else if (excit_class(imono) == "a-v" .and.hessmat(imono,imono).gt.0.d0)then ! active --> virtual rotation
n_orb_swap += 1
orb_swap(1,n_orb_swap) = jorb ! virtual
orb_swap(2,n_orb_swap) = iorb ! active
index_orb_swap(n_orb_swap) = imono
endif
enddo
integer,allocatable :: orb_swap_tmp(:,:)
allocate(orb_swap_tmp(2,dim_n_max_overlap))
do i = 1, n_orb_swap
orb_swap_tmp(1,i) = orb_swap(1,i)
orb_swap_tmp(2,i) = orb_swap(2,i)
enddo
integer(bit_kind), allocatable :: det_i(:),det_j(:)
allocate(det_i(N_int),det_j(N_int))
logical, allocatable :: good_orb_rot(:)
allocate(good_orb_rot(n_orb_swap))
integer, allocatable :: index_orb_swap_tmp(:)
allocate(index_orb_swap_tmp(dim_n_max_overlap))
index_orb_swap_tmp = index_orb_swap
good_orb_rot = .True.
integer :: icount,k
do i = 1, n_orb_swap
if(.not.good_orb_rot(i))cycle
det_i = 0_bit_kind
call set_bit_to_integer(orb_swap(1,i),det_i,N_int)
call set_bit_to_integer(orb_swap(2,i),det_i,N_int)
do j = i+1, n_orb_swap
det_j = 0_bit_kind
call set_bit_to_integer(orb_swap(1,j),det_j,N_int)
call set_bit_to_integer(orb_swap(2,j),det_j,N_int)
icount = 0
do k = 1, N_int
icount += popcnt(ior(det_i(k),det_j(k)))
enddo
if (icount.ne.4)then
good_orb_rot(i) = .False.
good_orb_rot(j) = .False.
exit
endif
enddo
enddo
icount = n_orb_swap
n_orb_swap = 0
do i = 1, icount
if(good_orb_rot(i))then
n_orb_swap += 1
index_orb_swap(n_orb_swap) = index_orb_swap_tmp(i)
orb_swap(1,n_orb_swap) = orb_swap_tmp(1,i)
orb_swap(2,n_orb_swap) = orb_swap_tmp(2,i)
endif
enddo
if(n_orb_swap.gt.0)then
print*,'n_orb_swap = ',n_orb_swap
endif
do i = 1, n_orb_swap
print*,'imono = ',index_orb_swap(i)
print*,orb_swap(1,i),'-->',orb_swap(2,i)
enddo
END_PROVIDER
BEGIN_PROVIDER [double precision, switch_mo_coef, (ao_num,mo_num)]
implicit none
integer :: i,j,iorb,jorb
switch_mo_coef = NatOrbsFCI
do i = 1, n_orb_swap
iorb = orb_swap(1,i)
jorb = orb_swap(2,i)
do j = 1, ao_num
switch_mo_coef(j,jorb) = NatOrbsFCI(j,iorb)
enddo
do j = 1, ao_num
switch_mo_coef(j,iorb) = NatOrbsFCI(j,jorb)
enddo
enddo
END_PROVIDER

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BEGIN_PROVIDER [real*8, etwo]
&BEGIN_PROVIDER [real*8, eone]
&BEGIN_PROVIDER [real*8, eone_bis]
&BEGIN_PROVIDER [real*8, etwo_bis]
&BEGIN_PROVIDER [real*8, etwo_ter]
&BEGIN_PROVIDER [real*8, ecore]
&BEGIN_PROVIDER [real*8, ecore_bis]
implicit none
integer :: t,u,v,x,i,ii,tt,uu,vv,xx,j,jj,t3,u3,v3,x3
real*8 :: e_one_all,e_two_all
e_one_all=0.D0
e_two_all=0.D0
do i=1,n_core_inact_orb
ii=list_core_inact(i)
e_one_all+=2.D0*mo_one_e_integrals(ii,ii)
do j=1,n_core_inact_orb
jj=list_core_inact(j)
e_two_all+=2.D0*bielec_PQxx(ii,ii,j,j)-bielec_PQxx(ii,jj,j,i)
end do
do t=1,n_act_orb
tt=list_act(t)
t3=t+n_core_inact_orb
do u=1,n_act_orb
uu=list_act(u)
u3=u+n_core_inact_orb
e_two_all+=D0tu(t,u)*(2.D0*bielec_PQxx(tt,uu,i,i) &
-bielec_PQxx(tt,ii,i,u3))
end do
end do
end do
do t=1,n_act_orb
tt=list_act(t)
do u=1,n_act_orb
uu=list_act(u)
e_one_all+=D0tu(t,u)*mo_one_e_integrals(tt,uu)
do v=1,n_act_orb
v3=v+n_core_inact_orb
do x=1,n_act_orb
x3=x+n_core_inact_orb
e_two_all +=P0tuvx(t,u,v,x)*bielec_PQxx(tt,uu,v3,x3)
end do
end do
end do
end do
ecore =nuclear_repulsion
ecore_bis=nuclear_repulsion
do i=1,n_core_inact_orb
ii=list_core_inact(i)
ecore +=2.D0*mo_one_e_integrals(ii,ii)
ecore_bis+=2.D0*mo_one_e_integrals(ii,ii)
do j=1,n_core_inact_orb
jj=list_core_inact(j)
ecore +=2.D0*bielec_PQxx(ii,ii,j,j)-bielec_PQxx(ii,jj,j,i)
ecore_bis+=2.D0*bielec_PxxQ(ii,i,j,jj)-bielec_PxxQ(ii,j,j,ii)
end do
end do
eone =0.D0
eone_bis=0.D0
etwo =0.D0
etwo_bis=0.D0
etwo_ter=0.D0
do t=1,n_act_orb
tt=list_act(t)
t3=t+n_core_inact_orb
do u=1,n_act_orb
uu=list_act(u)
u3=u+n_core_inact_orb
eone +=D0tu(t,u)*mo_one_e_integrals(tt,uu)
eone_bis+=D0tu(t,u)*mo_one_e_integrals(tt,uu)
do i=1,n_core_inact_orb
ii=list_core_inact(i)
eone +=D0tu(t,u)*(2.D0*bielec_PQxx(tt,uu,i,i) &
-bielec_PQxx(tt,ii,i,u3))
eone_bis+=D0tu(t,u)*(2.D0*bielec_PxxQ(tt,u3,i,ii) &
-bielec_PxxQ(tt,i,i,uu))
end do
do v=1,n_act_orb
vv=list_act(v)
v3=v+n_core_inact_orb
do x=1,n_act_orb
xx=list_act(x)
x3=x+n_core_inact_orb
real*8 :: h1,h2,h3
h1=bielec_PQxx(tt,uu,v3,x3)
h2=bielec_PxxQ(tt,u3,v3,xx)
h3=bielecCI(t,u,v,xx)
etwo +=P0tuvx(t,u,v,x)*h1
etwo_bis+=P0tuvx(t,u,v,x)*h2
etwo_ter+=P0tuvx(t,u,v,x)*h3
if ((h1.ne.h2).or.(h1.ne.h3)) then
write(6,9901) t,u,v,x,h1,h2,h3
9901 format('aie: ',4I4,3E20.12)
end if
end do
end do
end do
end do
END_PROVIDER

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BEGIN_PROVIDER [real*8, gradvec_tc_r, (0:3,nMonoEx)]
&BEGIN_PROVIDER [real*8, gradvec_tc_l, (0:3,nMonoEx)]
BEGIN_DOC
! gradvec_tc_r(0:3,i) = <Chi_0| H E_q^p(i) |Phi_0>
!
! gradvec_tc_l(0:3,i) = <Chi_0| E_p^q(i) H |Phi_0>
!
! where the indices "i" corresponds to E_q^p(i)
!
! i = mat_idx_c_a(q,p)
!
! and gradvec_tc_r/l(0) = full matrix element
!
! gradvec_tc_r/l(1) = one-body part
! gradvec_tc_r/l(2) = two-body part
! gradvec_tc_r/l(3) = three-body part
END_DOC
implicit none
integer :: ii,tt,aa,indx
integer :: i,t,a,fff
double precision :: res_l(0:3), res_r(0:3)
gradvec_tc_l = 0.d0
gradvec_tc_r = 0.d0
! computing the core/inactive --> virtual orbitals gradients
do i=1,n_core_inact_orb
ii=list_core_inact(i)
do t=1,n_act_orb
tt=list_act(t)
indx = mat_idx_c_a(i,t)
call gradvec_tc_it(ii,tt,res_l,res_r)
do fff = 0,3
gradvec_tc_l(fff,indx)=res_l(fff)
gradvec_tc_r(fff,indx)=res_r(fff)
enddo
end do
end do
do i=1,n_core_inact_orb
ii=list_core_inact(i)
do a=1,n_virt_orb
indx = mat_idx_c_v(i,a)
aa=list_virt(a)
call gradvec_tc_ia(ii,aa,res_l,res_r)
do fff = 0,3
gradvec_tc_l(fff,indx)=res_l(fff)
gradvec_tc_r(fff,indx)=res_r(fff)
enddo
end do
end do
do t=1,n_act_orb
tt=list_act(t)
do a=1,n_virt_orb
aa=list_virt(a)
indx = mat_idx_a_v(t,a)
call gradvec_tc_ta(tt,aa,res_l, res_r)
do fff = 0,3
gradvec_tc_l(fff,indx)=res_l(fff)
gradvec_tc_r(fff,indx)=res_r(fff)
enddo
end do
end do
END_PROVIDER
subroutine gradvec_tc_ia(i,a,res_l, res_r)
implicit none
BEGIN_DOC
! doubly occupied --> virtual TC gradient
!
! Corresponds to res_r = <X0|H E_i^a|Phi_0>,
!
! res_l = <X0|E_a^i H|Phi_0>
END_DOC
integer, intent(in) :: i,a
double precision, intent(out) :: res_l(0:3), res_r(0:3)
res_l = 0.d0
res_r = 0.d0
res_l(1) = -2 * mo_bi_ortho_tc_one_e(a,i)
res_r(1) = -2 * mo_bi_ortho_tc_one_e(i,a)
end
subroutine gradvec_tc_it(i,t,res_l, res_r)
implicit none
BEGIN_DOC
! doubly occupied --> active TC gradient
!
! Corresponds to res_r = <X0|H E_i^t|Phi_0>
!
! res_l = <X0|E_t^i H |Phi_0>
END_DOC
integer, intent(in) :: i,t
double precision, intent(out) :: res_l(0:3),res_r(0:3)
integer :: rr,r,ss,s,m,mm
double precision :: dm
res_r = 0.d0
res_l = 0.d0
res_r(1) += -2.d0 * mo_bi_ortho_tc_one_e(i,t)
res_l(1) += 2.D0 * mo_bi_ortho_tc_one_e(t,i)
do rr = 1, n_act_orb
r = list_act(rr)
res_r(1) += mo_bi_ortho_tc_one_e(i,r) * tc_transition_matrix_mo(t,r,1,1)
res_l(1) += -mo_bi_ortho_tc_one_e(r,i) * tc_transition_matrix_mo(r,t,1,1)
enddo
end
subroutine gradvec_tc_ta(t,a,res_l, res_r)
implicit none
BEGIN_DOC
! active --> virtual TC gradient
!
! Corresponds to res_r = <X0|H E_t^a|Phi_0>
!
! res_l = <X0|E_a^t H |Phi_0>
END_DOC
integer, intent(in) :: t,a
double precision, intent(out) :: res_l(0:3),res_r(0:3)
integer :: rr,r,m
double precision :: dm
res_r = 0.d0
res_l = 0.d0
do rr = 1, n_act_orb
r = list_act(rr)
res_l(1) += mo_bi_ortho_tc_one_e(a,r) * tc_transition_matrix_mo(t,r,1,1)
res_r(1) += -mo_bi_ortho_tc_one_e(r,a) * tc_transition_matrix_mo(r,t,1,1)
enddo
end

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BEGIN_PROVIDER [real*8, gradvec_detail_right_old, (0:3,nMonoEx)]
&BEGIN_PROVIDER [real*8, gradvec_detail_left_old, (0:3,nMonoEx)]
BEGIN_DOC
! calculate the orbital gradient <Psi| H E_pq |Psi> by hand, i.e. for
! each determinant I we determine the string E_pq |I> (alpha and beta
! separately) and generate <Psi|H E_pq |I>
! sum_I c_I <Psi|H E_pq |I> is then the pq component of the orbital
! gradient
! E_pq = a^+_pa_q + a^+_Pa_Q
END_DOC
implicit none
integer :: ii,tt,aa,indx,ihole,ipart,istate,ll
real*8 :: res_l(0:3), res_r(0:3)
do ii = 1, n_core_inact_orb
ihole = list_core_inact(ii)
do aa = 1, n_virt_orb
ipart = list_virt(aa)
indx = mat_idx_c_v(ii,aa)
call calc_grad_elem_h_tc(ihole,ipart,res_l, res_r)
do ll = 0, 3
gradvec_detail_left_old (ll,indx)=res_l(ll)
gradvec_detail_right_old(ll,indx)=res_r(ll)
enddo
enddo
enddo
do ii = 1, n_core_inact_orb
ihole = list_core_inact(ii)
do tt = 1, n_act_orb
ipart = list_act(tt)
indx = mat_idx_c_a(ii,tt)
call calc_grad_elem_h_tc(ihole,ipart,res_l, res_r)
do ll = 0, 3
gradvec_detail_left_old (ll,indx)=res_l(ll)
gradvec_detail_right_old(ll,indx)=res_r(ll)
enddo
enddo
enddo
do tt = 1, n_act_orb
ihole = list_act(tt)
do aa = 1, n_virt_orb
ipart = list_virt(aa)
indx = mat_idx_a_v(tt,aa)
call calc_grad_elem_h_tc(ihole,ipart,res_l, res_r)
do ll = 0, 3
gradvec_detail_left_old (ll,indx)=res_l(ll)
gradvec_detail_right_old(ll,indx)=res_r(ll)
enddo
enddo
enddo
real*8 :: norm_grad_left, norm_grad_right
norm_grad_left=0.d0
norm_grad_right=0.d0
do indx=1,nMonoEx
norm_grad_left+=gradvec_detail_left_old(0,indx)*gradvec_detail_left_old(0,indx)
norm_grad_right+=gradvec_detail_right_old(0,indx)*gradvec_detail_right_old(0,indx)
end do
norm_grad_left=sqrt(norm_grad_left)
norm_grad_right=sqrt(norm_grad_right)
! if (bavard) then
write(6,*)
write(6,*) ' Norm of the LEFT orbital gradient (via <0|EH|0>) : ', norm_grad_left
write(6,*) ' Norm of the RIGHT orbital gradient (via <0|HE|0>) : ', norm_grad_right
write(6,*)
! endif
END_PROVIDER
subroutine calc_grad_elem_h_tc(ihole,ipart,res_l, res_r)
BEGIN_DOC
! Computes the gradient with respect to orbital rotation BRUT FORCE
!
! res_l = <Chi| E_qp H^tc | Phi>
!
! res_r = <Chi| H^tc E_pq | Phi>
!
! q=hole, p=particle. NOTE that on res_l it is E_qp and on res_r it is E_pq
!
! res_l(0) = total matrix element, res_l(1) = one-electron part,
!
! res_l(2) = two-electron part, res_l(3) = three-electron part
!
END_DOC
implicit none
integer, intent(in) :: ihole,ipart
double precision, intent(out) :: res_l(0:3), res_r(0:3)
integer :: mu,iii,ispin,ierr,nu,istate,ll
integer(bit_kind), allocatable :: det_mu(:,:),det_mu_ex(:,:)
real*8 :: chi_H_mu_ex_array(0:3,N_states),mu_ex_H_phi_array(0:3,N_states),phase
allocate(det_mu(N_int,2))
allocate(det_mu_ex(N_int,2))
res_l=0.D0
res_r=0.D0
do mu=1,n_det
! get the string of the determinant |mu>
call det_extract(det_mu,mu,N_int)
do ispin=1,2
! do the monoexcitation on it: |det_mu_ex> = a^dagger_{p,ispin} a_{q,ispin} |mu>
call det_copy(det_mu,det_mu_ex,N_int)
call do_signed_mono_excitation(det_mu,det_mu_ex,nu &
,ihole,ipart,ispin,phase,ierr)
! |det_mu_ex> = a^dagger_{p,ispin} a_{q,ispin} |mu>
if (ierr.eq.1) then
call i_H_tc_psi_phi(det_mu_ex,psi_det,psi_l_coef_bi_ortho,psi_r_coef_bi_ortho,N_int &
,N_det,psi_det_size,N_states,chi_H_mu_ex_array,mu_ex_H_phi_array)
! chi_H_mu_ex_array = <Chi|H E_qp |mu >
! mu_ex_H_phi_array = <mu |E_qp H |Phi>
do istate=1,N_states
do ll = 0,3 ! loop over the body components (1e,2e,3e)
!res_l = \sum_mu c_mu^l <mu|E_qp H |Phi> = <Chi|E_qp H |Phi>
res_l(ll)+= mu_ex_H_phi_array(ll,istate)*psi_l_coef_bi_ortho(mu,istate)*phase
!res_r = \sum_mu c_mu^r <Chi|H E_qp |mu> = <Chi|H E_qp |Phi>
res_r(ll)+= chi_H_mu_ex_array(ll,istate)*psi_r_coef_bi_ortho(mu,istate)*phase
enddo
end do
end if
end do
end do
! state-averaged gradient
res_l*=1.d0/dble(N_states)
res_r*=1.d0/dble(N_states)
end

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use bitmasks
BEGIN_PROVIDER [ integer, nMonoEx ]
BEGIN_DOC
! Number of single excitations
END_DOC
implicit none
nMonoEx=n_core_inact_orb*n_act_orb+n_core_inact_orb*n_virt_orb+n_act_orb*n_virt_orb
END_PROVIDER
BEGIN_PROVIDER [integer, n_c_a_prov]
&BEGIN_PROVIDER [integer, n_c_v_prov]
&BEGIN_PROVIDER [integer, n_a_v_prov]
implicit none
n_c_a_prov = n_core_inact_orb * n_act_orb
n_c_v_prov = n_core_inact_orb * n_virt_orb
n_a_v_prov = n_act_orb * n_virt_orb
END_PROVIDER
BEGIN_PROVIDER [integer, excit, (2,nMonoEx)]
&BEGIN_PROVIDER [character*3, excit_class, (nMonoEx)]
&BEGIN_PROVIDER [integer, list_idx_c_a, (3,n_c_a_prov) ]
&BEGIN_PROVIDER [integer, list_idx_c_v, (3,n_c_v_prov) ]
&BEGIN_PROVIDER [integer, list_idx_a_v, (3,n_a_v_prov) ]
&BEGIN_PROVIDER [integer, mat_idx_c_a, (n_core_inact_orb,n_act_orb)
&BEGIN_PROVIDER [integer, mat_idx_c_v, (n_core_inact_orb,n_virt_orb)
&BEGIN_PROVIDER [integer, mat_idx_a_v, (n_act_orb,n_virt_orb)
BEGIN_DOC
! a list of the orbitals involved in the excitation
END_DOC
implicit none
integer :: i,t,a,ii,tt,aa,indx,indx_tmp
indx=0
indx_tmp = 0
do ii=1,n_core_inact_orb
i=list_core_inact(ii)
do tt=1,n_act_orb
t=list_act(tt)
indx+=1
excit(1,indx)=i
excit(2,indx)=t
excit_class(indx)='c-a'
indx_tmp += 1
list_idx_c_a(1,indx_tmp) = indx
list_idx_c_a(2,indx_tmp) = ii
list_idx_c_a(3,indx_tmp) = tt
mat_idx_c_a(ii,tt) = indx
end do
end do
indx_tmp = 0
do ii=1,n_core_inact_orb
i=list_core_inact(ii)
do aa=1,n_virt_orb
a=list_virt(aa)
indx+=1
excit(1,indx)=i
excit(2,indx)=a
excit_class(indx)='c-v'
indx_tmp += 1
list_idx_c_v(1,indx_tmp) = indx
list_idx_c_v(2,indx_tmp) = ii
list_idx_c_v(3,indx_tmp) = aa
mat_idx_c_v(ii,aa) = indx
end do
end do
indx_tmp = 0
do tt=1,n_act_orb
t=list_act(tt)
do aa=1,n_virt_orb
a=list_virt(aa)
indx+=1
excit(1,indx)=t
excit(2,indx)=a
excit_class(indx)='a-v'
indx_tmp += 1
list_idx_a_v(1,indx_tmp) = indx
list_idx_a_v(2,indx_tmp) = tt
list_idx_a_v(3,indx_tmp) = aa
mat_idx_a_v(tt,aa) = indx
end do
end do
! if (bavard) then
write(6,*) ' Filled the table of the Monoexcitations '
do indx=1,nMonoEx
write(6,*) ' ex ',indx,' : ',excit(1,indx),' -> ' &
,excit(2,indx),' ',excit_class(indx)
end do
! end if
END_PROVIDER

48
src/ccsd/ccsd_space_orb_sub_chol.irp.f
View File

@ -1024,56 +1024,26 @@ subroutine compute_A1_chol(nO,nV,t1,t2,tau,A1)
integer :: a,tmp_a,b,k,l,c,d,tmp_c,tmp_d,i,j,u,v, beta
double precision, allocatable :: X_vooo(:,:,:,:), Y_oooo(:,:,:,:)
allocate(X_vooo(nV,nO,nO,nO), Y_oooo(nO,nO,nO,nO))
double precision, allocatable :: Y_oooo(:,:,:,:)
allocate(Y_oooo(nO,nO,nO,nO))
! A1(u,v,i,j) = cc_space_v_oooo(u,v,i,j)
!$omp parallel &
!$omp shared(nO,nV,A1,cc_space_v_oooo,cc_space_v_ovoo,X_vooo) &
!$omp private(u,v,i,j) &
!$omp default(none)
!$omp do collapse(2)
do j = 1, nO
do i = 1, nO
do v = 1, nO
do u = 1, nO
A1(u,v,i,j) = cc_space_v_oooo(u,v,i,j)
enddo
enddo
enddo
enddo
!$omp end do nowait
! A1(u,v,i,j) += cc_space_v_ovoo(u,a,i,j) * t1(v,a) &
!$omp do collapse(2)
do j = 1, nO
do i = 1, nO
do u = 1, nO
do a = 1, nV
X_vooo(a,u,i,j) = cc_space_v_ovoo(u,a,i,j)
enddo
enddo
enddo
enddo
!$omp end do
!$omp end parallel
call dgemm('N','N', nO, nO*nO*nO, nV, &
1d0, t1 , size(t1,1), &
X_vooo, size(X_vooo,1), &
cc_space_v_vooo, size(cc_space_v_vooo,1), &
0d0, Y_oooo, size(Y_oooo,1))
!$omp parallel &
!$omp shared(nO,nV,A1,Y_oooo) &
!$omp private(u,v,i,j) &
!$omp default(none)
!$omp default(shared)
!$omp do collapse(2)
do j = 1, nO
do i = 1, nO
do v = 1, nO
do u = 1, nO
A1(u,v,i,j) = A1(u,v,i,j) + Y_oooo(v,u,i,j)
A1(u,v,i,j) = cc_space_v_oooo(u,v,i,j) + Y_oooo(v,u,j,i) + Y_oooo(u,v,i,j)
enddo
enddo
enddo
@ -1081,13 +1051,7 @@ subroutine compute_A1_chol(nO,nV,t1,t2,tau,A1)
!$omp end do
!$omp end parallel
deallocate(X_vooo,Y_oooo)
! A1(u,v,i,j) += cc_space_v_vooo(a,v,i,j) * t1(u,a)
call dgemm('N','N', nO, nO*nO*nO, nV, &
1d0, t1 , size(t1,1), &
cc_space_v_vooo, size(cc_space_v_vooo,1), &
1d0, A1 , size(A1,1))
deallocate(Y_oooo)
! A1(u,v,i,j) += cc_space_v_vvoo(a,b,i,j) * tau(u,v,a,b)
call dgemm('N','N', nO*nO, nO*nO, nV*nV, &

8
src/cipsi_tc_bi_ortho/get_d0_good.irp.f
View File

@ -53,7 +53,7 @@ subroutine get_d0_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if (hij == (0.d0,0.d0)) cycle
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_r(k, p1, p2) = mat_r(k, p1, p2) + coefs(k,1) * hij ! HOTSPOT
mat_r(k, p1, p2) = mat_r(k, p1, p2) + coefs(k,2) * hij ! HOTSPOT
enddo
end do
!!!!!!!!!! <phi|H|alpha>
@ -72,7 +72,7 @@ subroutine get_d0_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if (hji == (0.d0,0.d0)) cycle
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_l(k, p1, p2) = mat_l(k, p1, p2) + coefs(k,2) * hji ! HOTSPOT
mat_l(k, p1, p2) = mat_l(k, p1, p2) + coefs(k,1) * hji ! HOTSPOT
enddo
end do
end do
@ -109,7 +109,7 @@ subroutine get_d0_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
end if
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,1) * hij
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,2) * hij
enddo
end do
@ -128,7 +128,7 @@ subroutine get_d0_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
end if
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,2) * hji
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,1) * hji
enddo
end do
end do

36
src/cipsi_tc_bi_ortho/get_d1_good.irp.f
View File

@ -76,7 +76,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hij = hij * get_phase_bi(phasemask, ma, ma, putj, p1, hfix, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
tmp_rowij(k,putj) = tmp_rowij(k,putj) + hij * coefs(k,1)
tmp_rowij(k,putj) = tmp_rowij(k,putj) + hij * coefs(k,2)
enddo
endif
end do
@ -88,7 +88,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hij = hij * get_phase_bi(phasemask, ma, ma, hfix, p1, putj, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
tmp_rowij(k,putj) = tmp_rowij(k,putj) + hij * coefs(k,1)
tmp_rowij(k,putj) = tmp_rowij(k,putj) + hij * coefs(k,2)
enddo
endif
end do
@ -114,7 +114,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hji = hji * get_phase_bi(phasemask, ma, ma, putj, p1, hfix, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
tmp_rowji(k,putj) = tmp_rowji(k,putj) + hji * coefs(k,2)
tmp_rowji(k,putj) = tmp_rowji(k,putj) + hji * coefs(k,1)
enddo
endif
end do
@ -126,7 +126,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hji = hji * get_phase_bi(phasemask, ma, ma, hfix, p1, putj, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
tmp_rowji(k,putj) = tmp_rowji(k,putj) + hji * coefs(k,2)
tmp_rowji(k,putj) = tmp_rowji(k,putj) + hji * coefs(k,1)
enddo
endif
end do
@ -169,7 +169,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hij = hij * get_phase_bi(phasemask, ma, mi, hfix, p2, puti, pfix, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
tmp_rowij(k,puti) = tmp_rowij(k,puti) + hij * coefs(k,1)
tmp_rowij(k,puti) = tmp_rowij(k,puti) + hij * coefs(k,2)
enddo
endif
end if
@ -180,7 +180,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if (hij /= 0.d0) then
hij = hij * get_phase_bi(phasemask, ma, mi, hfix, p1, puti, pfix, N_int)
do k=1,N_states
tmp_rowij2(k,puti) = tmp_rowij2(k,puti) + hij * coefs(k,1)
tmp_rowij2(k,puti) = tmp_rowij2(k,puti) + hij * coefs(k,2)
enddo
endif
end if
@ -211,7 +211,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hji = hji * get_phase_bi(phasemask, ma, mi, hfix, p2, puti, pfix, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
tmp_rowji(k,puti) = tmp_rowji(k,puti) + hji * coefs(k,2)
tmp_rowji(k,puti) = tmp_rowji(k,puti) + hji * coefs(k,1)
enddo
endif
end if
@ -222,7 +222,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if (hji /= 0.d0) then
hji = hji * get_phase_bi(phasemask, ma, mi, hfix, p1, puti, pfix, N_int)
do k=1,N_states
tmp_rowji2(k,puti) = tmp_rowji2(k,puti) + hji * coefs(k,2)
tmp_rowji2(k,puti) = tmp_rowji2(k,puti) + hji * coefs(k,1)
enddo
endif
end if
@ -265,7 +265,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hij = hij_cache(putj,1) - hij_cache(putj,2)
if (hij /= 0.d0) then
hij = hij * get_phase_bi(phasemask, ma, ma, putj, p1, hfix, p2, N_int)
tmp_rowij(:,putj) = tmp_rowij(:,putj) + hij * coefs(:,1)
tmp_rowij(:,putj) = tmp_rowij(:,putj) + hij * coefs(:,2)
endif
end do
do putj=hfix+1,mo_num
@ -274,7 +274,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hij = hij_cache(putj,2) - hij_cache(putj,1)
if (hij /= 0.d0) then
hij = hij * get_phase_bi(phasemask, ma, ma, hfix, p1, putj, p2, N_int)
tmp_rowij(:,putj) = tmp_rowij(:,putj) + hij * coefs(:,1)
tmp_rowij(:,putj) = tmp_rowij(:,putj) + hij * coefs(:,2)
endif
end do
@ -293,7 +293,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hji = hji_cache(putj,1) - hji_cache(putj,2)
if (hji /= 0.d0) then
hji = hji * get_phase_bi(phasemask, ma, ma, putj, p1, hfix, p2, N_int)
tmp_rowji(:,putj) = tmp_rowji(:,putj) + hji * coefs(:,2)
tmp_rowji(:,putj) = tmp_rowji(:,putj) + hji * coefs(:,1)
endif
end do
do putj=hfix+1,mo_num
@ -302,7 +302,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hji = hji_cache(putj,2) - hji_cache(putj,1)
if (hji /= 0.d0) then
hji = hji * get_phase_bi(phasemask, ma, ma, hfix, p1, putj, p2, N_int)
tmp_rowji(:,putj) = tmp_rowji(:,putj) + hji * coefs(:,2)
tmp_rowji(:,putj) = tmp_rowji(:,putj) + hji * coefs(:,1)
endif
end do
@ -342,7 +342,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hij = hij * get_phase_bi(phasemask, mi, ma, hfix, pfix, puti, p1, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
tmp_rowij(k,puti) = tmp_rowij(k,puti) + hij * coefs(k,1)
tmp_rowij(k,puti) = tmp_rowij(k,puti) + hij * coefs(k,2)
enddo
endif
end if
@ -353,7 +353,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if (hij /= 0.d0) then
hij = hij * get_phase_bi(phasemask, mi, ma, hfix, pfix, puti, p2, N_int)
do k=1,N_states
tmp_rowij2(k,puti) = tmp_rowij2(k,puti) + hij * coefs(k,1)
tmp_rowij2(k,puti) = tmp_rowij2(k,puti) + hij * coefs(k,2)
enddo
endif
end if
@ -385,7 +385,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hji = hji * get_phase_bi(phasemask, mi, ma, hfix, pfix, puti, p1, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
tmp_rowji(k,puti) = tmp_rowji(k,puti) + hji * coefs(k,2)
tmp_rowji(k,puti) = tmp_rowji(k,puti) + hji * coefs(k,1)
enddo
endif
end if
@ -396,7 +396,7 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if (hji /= 0.d0) then
hji = hji * get_phase_bi(phasemask, mi, ma, hfix, pfix, puti, p2, N_int)
do k=1,N_states
tmp_rowji2(k,puti) = tmp_rowji2(k,puti) + hji * coefs(k,2)
tmp_rowji2(k,puti) = tmp_rowji2(k,puti) + hji * coefs(k,1)
enddo
endif
end if
@ -445,8 +445,8 @@ subroutine get_d1_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
do k=1,N_states
! take conjugate to get contribution to <alpha|H|psi> instead of <psi|H|alpha>
! mat_r(k, p1, p2) = mat_r(k, p1, p2) + coefs(k,1) * dconjg(hij)
mat_r(k, p1, p2) = mat_r(k, p1, p2) + coefs(k,1) * hij
mat_l(k, p1, p2) = mat_l(k, p1, p2) + coefs(k,2) * hji
mat_r(k, p1, p2) = mat_r(k, p1, p2) + coefs(k,2) * hij
mat_l(k, p1, p2) = mat_l(k, p1, p2) + coefs(k,1) * hji
enddo
end do
end do

28
src/cipsi_tc_bi_ortho/get_d2_good.irp.f
View File

@ -79,12 +79,12 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if(ma == 1) then ! if particle spins are (alpha,alpha,alpha,beta), then puti is beta and putj is alpha
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_r(k, putj, puti) = mat_r(k, putj, puti) + coefs(k,1) * hij
mat_r(k, putj, puti) = mat_r(k, putj, puti) + coefs(k,2) * hij
enddo
else ! if particle spins are (beta,beta,beta,alpha), then puti is alpha and putj is beta
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,1) * hij
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,2) * hij
enddo
end if
end do
@ -103,12 +103,12 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if(ma == 1) then ! if particle spins are (alpha,alpha,alpha,beta), then puti is beta and putj is alpha
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_l(k, putj, puti) = mat_l(k, putj, puti) + coefs(k,2) * hji
mat_l(k, putj, puti) = mat_l(k, putj, puti) + coefs(k,1) * hji
enddo
else ! if particle spins are (beta,beta,beta,alpha), then puti is alpha and putj is beta
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,2) * hji
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,1) * hji
enddo
end if
end do
@ -135,7 +135,7 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hij = hij * get_phase_bi(phasemask, 1, 2, h1, p1, h2, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,1) * hij
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,2) * hij
enddo
endif
end do
@ -154,7 +154,7 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hji = hji * get_phase_bi(phasemask, 1, 2, h1, p1, h2, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,2) * hji
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,1) * hji
enddo
endif
end do
@ -189,7 +189,7 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hij = hij * get_phase_bi(phasemask, ma, ma, h1, p1, h2, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_r(k, puti, putj) = mat_r(k, puti, putj) +coefs(k,1) * hij
mat_r(k, puti, putj) = mat_r(k, puti, putj) +coefs(k,2) * hij
enddo
end do
end do
@ -210,7 +210,7 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hji = hji * get_phase_bi(phasemask, ma, ma, h1, p1, h2, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_l(k, puti, putj) = mat_l(k, puti, putj) +coefs(k,2) * hji
mat_l(k, puti, putj) = mat_l(k, puti, putj) +coefs(k,1) * hji
enddo
end do
end do
@ -239,12 +239,12 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if (puti < putj) then
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,1) * hij
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,2) * hij
enddo
else
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_r(k, putj, puti) = mat_r(k, putj, puti) + coefs(k,1) * hij
mat_r(k, putj, puti) = mat_r(k, putj, puti) + coefs(k,2) * hij
enddo
endif
end do
@ -262,12 +262,12 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
if (puti < putj) then
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,2) * hji
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,1) * hji
enddo
else
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_l(k, putj, puti) = mat_l(k, putj, puti) + coefs(k,2) * hji
mat_l(k, putj, puti) = mat_l(k, putj, puti) + coefs(k,1) * hji
enddo
endif
end do
@ -290,7 +290,7 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hij = hij * get_phase_bi(phasemask, mi, mi, h1, p1, h2, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,1) * hij
mat_r(k, puti, putj) = mat_r(k, puti, putj) + coefs(k,2) * hij
enddo
end if
!! <phi|H|alpha>
@ -299,7 +299,7 @@ subroutine get_d2_new(gen, phasemask, bannedOrb, banned, mat_l, mat_r, mask, h,
hji = hji * get_phase_bi(phasemask, mi, mi, h1, p1, h2, p2, N_int)
!DIR$ LOOP COUNT AVG(4)
do k=1,N_states
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,2) * hji
mat_l(k, puti, putj) = mat_l(k, puti, putj) + coefs(k,1) * hji
enddo
end if
end if

35
src/cipsi_tc_bi_ortho/selection.irp.f
View File

@ -893,20 +893,45 @@ subroutine fill_buffer_double(i_generator, sp, h1, h2, bannedOrb, banned, fock_d
alpha_h_psi += alpha_h_i * psi_selectors_coef_tc(iii,1,1) ! right function
enddo
else if(debug_tc_pt2 == 2)then !! debugging the new version
! psi_h_alpha_tmp = 0.d0
! alpha_h_psi_tmp = 0.d0
! do iii = 1, N_det_selectors ! old version
! call htilde_mu_mat_opt_bi_ortho_no_3e(psi_selectors(1,1,iii), det, N_int, i_h_alpha)
! call htilde_mu_mat_opt_bi_ortho_no_3e(det, psi_selectors(1,1,iii), N_int, alpha_h_i)
! psi_h_alpha_tmp += i_h_alpha * psi_selectors_coef_tc(iii,1,1) ! left function
! alpha_h_psi_tmp += alpha_h_i * psi_selectors_coef_tc(iii,2,1) ! right function
! enddo
psi_h_alpha_tmp = mat_l(istate, p1, p2) ! new version
alpha_h_psi_tmp = mat_r(istate, p1, p2) ! new version
psi_h_alpha = 0.d0
alpha_h_psi = 0.d0
do iii = 1, N_det_selectors ! old version
call htilde_mu_mat_opt_bi_ortho_no_3e(psi_selectors(1,1,iii), det, N_int, i_h_alpha)
call htilde_mu_mat_opt_bi_ortho_no_3e(det, psi_selectors(1,1,iii), N_int, alpha_h_i)
psi_h_alpha += i_h_alpha * psi_selectors_coef_tc(iii,2,1) ! left function
alpha_h_psi += alpha_h_i * psi_selectors_coef_tc(iii,1,1) ! right function
do iii = 1, N_det ! old version
call htilde_mu_mat_opt_bi_ortho_no_3e(psi_det(1,1,iii), det, N_int, i_h_alpha)
call htilde_mu_mat_opt_bi_ortho_no_3e(det, psi_det(1,1,iii), N_int, alpha_h_i)
psi_h_alpha += i_h_alpha * psi_l_coef_bi_ortho(iii,1) ! left function
alpha_h_psi += alpha_h_i * psi_r_coef_bi_ortho(iii,1) ! right function
enddo
if(dabs(psi_h_alpha*alpha_h_psi/delta_E).gt.1.d-10)then
error = dabs(psi_h_alpha * alpha_h_psi - psi_h_alpha_tmp * alpha_h_psi_tmp)/dabs(psi_h_alpha * alpha_h_psi)
if(error.gt.1.d-2)then
call debug_det(det, N_int)
print*,'error =',error,psi_h_alpha * alpha_h_psi/delta_E,psi_h_alpha_tmp * alpha_h_psi_tmp/delta_E
print*,psi_h_alpha , alpha_h_psi
print*,psi_h_alpha_tmp , alpha_h_psi_tmp
print*,'selectors '
do iii = 1, N_det_selectors ! old version
print*,'iii',iii,psi_selectors_coef_tc(iii,1,1),psi_selectors_coef_tc(iii,2,1)
call htilde_mu_mat_opt_bi_ortho_no_3e(psi_selectors(1,1,iii), det, N_int, i_h_alpha)
call htilde_mu_mat_opt_bi_ortho_no_3e(det, psi_selectors(1,1,iii), N_int, alpha_h_i)
print*,i_h_alpha,alpha_h_i
call debug_det(psi_selectors(1,1,iii),N_int)
enddo
! print*,'psi_det '
! do iii = 1, N_det! old version
! print*,'iii',iii,psi_l_coef_bi_ortho(iii,1),psi_r_coef_bi_ortho(iii,1)
! call debug_det(psi_det(1,1,iii),N_int)
! enddo
stop
endif
endif
else

8
src/cisd/EZFIO.cfg
View File

@ -5,3 +5,11 @@ interface: ezfio
size: (determinants.n_states)
[lcc_energy]
type: double precision
doc: lccsd energy
interface: ezfio
size: (determinants.n_states)

1
src/cisd/NEED
View File

@ -1,3 +1,4 @@
selectors_full
single_ref_method
davidson_undressed
dav_general_mat

95
src/cisd/lccsd.irp.f Normal file
View File

@ -0,0 +1,95 @@
program lccsd
implicit none
BEGIN_DOC
! Linerarized CCSD
!
! This program takes a reference Slater determinant of ROHF-like occupancy,
!
! and performs all single and double excitations on top of it, disregarding
! spatial symmetry and compute the "n_states" lowest eigenstates of that CI
! matrix (see :option:`determinants n_states`).
!
! This program can be useful in many cases:
!
! * **Ground state calculation**: if even after a :c:func:`cis` calculation, natural
! orbitals (see :c:func:`save_natorb`) and then :c:func:`scf` optimization, you are not sure to have the lowest scf
! solution,
! do the same strategy with the :c:func:`cisd` executable instead of the :c:func:`cis` exectuable to generate the natural
! orbitals as a guess for the :c:func:`scf`.
!
!
!
! * **Excited states calculations**: the lowest excited states are much likely to
! be dominanted by single- or double-excitations.
! Therefore, running a :c:func:`cisd` will save the "n_states" lowest states within
! the CISD space
! in the |EZFIO| directory, which can afterward be used as guess wave functions
! for a further multi-state fci calculation if you specify "read_wf" = True
! before running the fci executable (see :option:`determinants read_wf`).
! Also, if you specify "s2_eig" = True, the cisd will only retain states
! having the good value :math:`S^2` value
! (see :option:`determinants expected_s2` and :option:`determinants s2_eig`).
! If "s2_eig" = False, it will take the lowest n_states, whatever
! multiplicity they are.
!
!
!
! Note: if you would like to discard some orbitals, use
! :ref:`qp_set_mo_class` to specify:
!
! * "core" orbitals which will be always doubly occupied
!
! * "act" orbitals where an electron can be either excited from or to
!
! * "del" orbitals which will be never occupied
!
END_DOC
PROVIDE N_states
read_wf = .False.
TOUCH read_wf
call run
end
subroutine run
implicit none
if(pseudo_sym)then
call H_apply_cisd_sym
else
call H_apply_cisd
endif
call get_lccsd_2
end
subroutine get_lccsd_2
implicit none
integer :: i,k
double precision :: cisdq(N_states), delta_e
double precision,external :: diag_h_mat_elem
psi_coef = lccsd_coef
SOFT_TOUCH psi_coef
call save_wavefunction_truncated(save_threshold)
call ezfio_set_cisd_lcc_energy(lccsd_energies)
print *, 'N_det = ', N_det
print*,''
print*,'******************************'
print *, 'LCCSD Energies'
do i = 1,N_states
print *, i, lccsd_energies(i)
enddo
if (N_states > 1) then
print*,'******************************'
print*,'Excitation energies (au) (LCCSD)'
do i = 2, N_states
print*, i ,lccsd_energies(i) - lccsd_energies(1)
enddo
print*,''
print*,'******************************'
print*,'Excitation energies (eV) (LCCSD)'
do i = 2, N_states
print*, i ,(lccsd_energies(i) - lccsd_energies(1)) * ha_to_ev
enddo
endif
end

46
src/cisd/lccsd_prov.irp.f Normal file
View File

@ -0,0 +1,46 @@
BEGIN_PROVIDER [ double precision, lccsd_coef, (N_det, N_states)]
&BEGIN_PROVIDER [ double precision, lccsd_energies, (N_states)]
implicit none
double precision, allocatable :: Dress_jj(:), H_jj(:), u_in(:,:)
double precision :: ebefore, eafter, ecorr, thresh
integer :: i,it
logical :: converged
external H_u_0_nstates_openmp
allocate(Dress_jj(N_det),H_jj(N_det),u_in(N_det,N_states_diag))
thresh = 1.d-6
converged = .False.
Dress_jj = 0.d0
u_in = 0.d0
it = 0
! initial guess
do i = 1, N_states_diag
u_in(i,i) = 1.d0
enddo
do i = 1,N_det
call i_H_j(psi_det(1,1,i),psi_det(1,1,i),N_int,H_jj(i))
enddo
ebefore = H_jj(1)
do while (.not.converged)
it += 1
print*,'N_det = ',N_det
call davidson_general_ext_rout_diag_dressed(u_in,H_jj,Dress_jj,lccsd_energies,&
N_det,N_states,N_states_diag,converged,H_u_0_nstates_openmp)
ecorr = lccsd_energies(1) - H_jj(1)
print*,'---------------------'
print*,'it = ',it
print*,'ecorr = ',ecorr
Dress_jj(1) = 0.d0
do i = 2, N_det
if(ecorr + H_jj(i) .gt. H_jj(1))then
Dress_jj(i) = ecorr
endif
enddo
eafter = lccsd_energies(1)
converged = (dabs(eafter - ebefore).lt.thresh)
ebefore = eafter
enddo
do i = 1, N_states
lccsd_coef(1:N_det,i) = u_in(1:N_det,i)
enddo
END_PROVIDER

2
src/fci_tc_bi/selectors.irp.f
View File

@ -27,6 +27,8 @@ END_PROVIDER
implicit none
BEGIN_DOC
! Determinants on which we apply <i|H|psi> for perturbation.
! psi_selectors_coef_tc(iii,1,istate) = left coefficient of the iii determinant
! psi_selectors_coef_tc(iii,2,istate) = right coefficient of the iii determinant
END_DOC
integer :: i,k

93
src/tc_bi_ortho/h_tc_bi_ortho_psi.irp.f
View File

@ -90,3 +90,96 @@ subroutine htcdag_bi_ortho_calc_tdav_slow(v, u, N_st, sze)
end
subroutine i_H_tc_psi_phi(key,keys,coef_l,coef_r,Nint,Ndet,Ndet_max,Nstate,chi_H_i_array,i_H_phi_array)
use bitmasks
implicit none
BEGIN_DOC
! Computes $\langle i|H|Phi \rangle = \sum_J c^R_J \langle i | H | J \rangle$.
!
! AND $\langle Chi|H| i \rangle = \sum_J c^L_J \langle J | H | i \rangle$.
!
! CONVENTION: i_H_phi_array(0) = total matrix element,
!
! i_H_phi_array(1) = one-electron matrix element,
!
! i_H_phi_array(2) = two-electron matrix element,
!
! i_H_phi_array(3) = three-electron matrix element,
!
! Uses filter_connected_i_H_psi0 to get all the $|J \rangle$ to which $|i \rangle$
! is connected.
!
! The i_H_psi_minilist is much faster but requires to build the
! minilists.
END_DOC
integer, intent(in) :: Nint, Ndet,Ndet_max,Nstate
integer(bit_kind), intent(in) :: keys(Nint,2,Ndet)
integer(bit_kind), intent(in) :: key(Nint,2)
double precision, intent(in) :: coef_l(Ndet_max,Nstate),coef_r(Ndet_max,Nstate)
double precision, intent(out) :: chi_H_i_array(0:3,Nstate),i_H_phi_array(0:3,Nstate)
integer :: i, ii,j
double precision :: phase
integer :: exc(0:2,2,2)
double precision :: hmono, htwoe, hthree, htot
integer, allocatable :: idx(:)
ASSERT (Nint > 0)
ASSERT (N_int == Nint)
ASSERT (Nstate > 0)
ASSERT (Ndet > 0)
ASSERT (Ndet_max >= Ndet)
allocate(idx(0:Ndet))
chi_H_i_array = 0.d0
i_H_phi_array = 0.d0
call filter_connected_i_H_psi0(keys,key,Nint,Ndet,idx)
if (Nstate == 1) then
do ii=1,idx(0)
i = idx(ii)
! computes <Chi|H_tc|i>
!DIR$ FORCEINLINE
call htilde_mu_mat_opt_bi_ortho(keys(1,1,i), key, Nint, hmono, htwoe, hthree, htot)
chi_H_i_array(0,1) = chi_H_i_array(0,1) + coef_l(i,1)*htot
chi_H_i_array(1,1) = chi_H_i_array(1,1) + coef_l(i,1)*hmono
chi_H_i_array(2,1) = chi_H_i_array(2,1) + coef_l(i,1)*htwoe
chi_H_i_array(3,1) = chi_H_i_array(3,1) + coef_l(i,1)*hthree
! computes <i|H_tc|Phi>
!DIR$ FORCEINLINE
call htilde_mu_mat_opt_bi_ortho(key,keys(1,1,i), Nint, hmono, htwoe, hthree, htot)
i_H_phi_array(0,1) = i_H_phi_array(0,1) + coef_r(i,1)*htot
i_H_phi_array(1,1) = i_H_phi_array(1,1) + coef_r(i,1)*hmono
i_H_phi_array(2,1) = i_H_phi_array(2,1) + coef_r(i,1)*htwoe
i_H_phi_array(3,1) = i_H_phi_array(3,1) + coef_r(i,1)*hthree
enddo
else
do ii=1,idx(0)
i = idx(ii)
! computes <Chi|H_tc|i>
!DIR$ FORCEINLINE
call htilde_mu_mat_opt_bi_ortho(keys(1,1,i), key, Nint, hmono, htwoe, hthree, htot)
do j = 1, Nstate
chi_H_i_array(0,j) = chi_H_i_array(0,j) + coef_l(i,j)*htot
chi_H_i_array(1,j) = chi_H_i_array(1,j) + coef_l(i,j)*hmono
chi_H_i_array(2,j) = chi_H_i_array(2,j) + coef_l(i,j)*htwoe
chi_H_i_array(3,j) = chi_H_i_array(3,j) + coef_l(i,j)*hthree
enddo
! computes <i|H_tc|Phi>
!DIR$ FORCEINLINE
call htilde_mu_mat_opt_bi_ortho(key,keys(1,1,i), Nint, hmono, htwoe, hthree, htot)
do j = 1, Nstate
i_H_phi_array(0,j) = i_H_phi_array(0,j) + coef_r(i,j)*htot
i_H_phi_array(1,j) = i_H_phi_array(1,j) + coef_r(i,j)*hmono
i_H_phi_array(2,j) = i_H_phi_array(2,j) + coef_r(i,j)*htwoe
i_H_phi_array(3,j) = i_H_phi_array(3,j) + coef_r(i,j)*hthree
enddo
enddo
endif
end

10
src/tc_bi_ortho/normal_ordered_old.irp.f
View File

@ -120,6 +120,13 @@ END_PROVIDER
subroutine give_aba_contraction(Nint, h1, h2, p1, p2, Ne, occ, hthree)
use bitmasks ! you need to include the bitmasks_module.f90 features
BEGIN_DOC
! give the contribution for a double excitation of opposite spin BUT averaged over spin
!
! it is the average of <p1_down p2_up |h1_down h2_up> and <p1_up p2_down |h1_up h2_down>
!
! because the orbitals h1,h2,p1,p2 are spatial orbitals and therefore can be of different spins
END_DOC
implicit none
integer, intent(in) :: Nint, h1, h2, p1, p2
@ -158,7 +165,8 @@ subroutine give_aba_contraction(Nint, h1, h2, p1, p2, Ne, occ, hthree)
call give_integrals_3_body_bi_ort(p2, i, p1, i, h2, h1, integral)
int_exc_12 = -1.d0 * integral
hthree += 1.d0 * int_direct - 0.5d0 * (int_exc_13 + int_exc_12)
hthree += 1.d0 * int_direct - 0.5d0 * (int_exc_13 + int_exc_12) ! spin average
! hthree += 1.d0 * int_direct - 1.0d0 * (int_exc_13 + int_exc_12)
enddo
return

2
src/tc_bi_ortho/slater_tc_3e_slow.irp.f
View File

@ -184,7 +184,7 @@ subroutine single_htilde_three_body_ints_bi_ort_slow(Nint, key_j, key_i, hthree)
ii = occ(i,s1)
do j = i+1, Ne(s1)
jj = occ(j,s1)
! ref = sym_3_e_int_from_6_idx_tensor(jj,ii,p1,jj,ii,h1)
! !ref = sym_3_e_int_from_6_idx_tensor(jj,ii,p1,jj,ii,h1)
hthree += three_e_single_parrallel_spin(jj,ii,p1,h1) ! USES THE 4-IDX TENSOR
enddo
enddo

5
src/tc_bi_ortho/tc_h_eigvectors.irp.f
View File

@ -328,6 +328,11 @@ end
TOUCH psi_r_coef_bi_ortho
call ezfio_set_tc_bi_ortho_psi_r_coef_bi_ortho(buffer)
deallocate(buffer)
! print*,'After diag'
! do i = 1, N_det! old version
! print*,'i',i,psi_l_coef_bi_ortho(i,1),psi_r_coef_bi_ortho(i,1)
! call debug_det(psi_det(1,1,i),N_int)
! enddo
END_PROVIDER

13
src/tc_bi_ortho/tc_natorb.irp.f
View File

@ -23,7 +23,7 @@
dm_tmp(1:mo_num,1:mo_num) = -tc_transition_matrix_mo(1:mo_num,1:mo_num,1,1)
print *, ' dm_tmp'
print *, ' Transition density matrix '
do i = 1, mo_num
fock_diag(i) = fock_matrix_tc_mo_tot(i,i)
write(*, '(100(F16.10,X))') -dm_tmp(:,i)
@ -32,8 +32,15 @@
thr_d = 1.d-6
thr_nd = 1.d-6
thr_deg = 1.d-3
call diag_mat_per_fock_degen( fock_diag, dm_tmp, mo_num, thr_d, thr_nd, thr_deg &
, natorb_tc_leigvec_mo, natorb_tc_reigvec_mo, natorb_tc_eigval)
if(n_core_orb.ne.0)then
! print*,'core orbitals'
! pause
call diag_mat_per_fock_degen_core( fock_diag, dm_tmp, list_core, n_core_orb, mo_num, thr_d, thr_nd, thr_deg &
, natorb_tc_leigvec_mo, natorb_tc_reigvec_mo, natorb_tc_eigval)
else
call diag_mat_per_fock_degen( fock_diag, dm_tmp, mo_num, thr_d, thr_nd, thr_deg &
, natorb_tc_leigvec_mo, natorb_tc_reigvec_mo, natorb_tc_eigval)
endif
! call non_hrmt_bieig( mo_num, dm_tmp&
! , natorb_tc_leigvec_mo, natorb_tc_reigvec_mo&
! , mo_num, natorb_tc_eigval )

8
src/tc_bi_ortho/tc_prop.irp.f
View File

@ -29,7 +29,7 @@
tc_transition_matrix_mo_alpha(m,m,istate,jstate)+= psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,jstate)
enddo
do p = 1, n_occ_ab(2) ! browsing the beta electrons
m = occ(p,1)
m = occ(p,2)
tc_transition_matrix_mo_beta(m,m,istate,jstate)+= psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,jstate)
enddo
else
@ -38,12 +38,14 @@
! Single alpha
h = exc(1,1,1) ! hole in psi_det(1,1,j)
p = exc(1,2,1) ! particle in psi_det(1,1,j)
tc_transition_matrix_mo_alpha(p,h,istate,jstate)+= phase * psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,jstate)
tc_transition_matrix_mo_alpha(p,h,istate,jstate)+= &
phase * psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,jstate)
else
! Single beta
h = exc(1,1,2) ! hole in psi_det(1,1,j)
p = exc(1,2,2) ! particle in psi_det(1,1,j)
tc_transition_matrix_mo_beta(p,h,istate,jstate)+= phase * psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,jstate)
tc_transition_matrix_mo_beta(p,h,istate,jstate)+= &
phase * psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,jstate)
endif
endif
enddo

43
src/tc_bi_ortho/test_normal_order.irp.f
View File

@ -33,7 +33,7 @@ subroutine test
integer :: h1,h2,p1,p2,s1,s2,i_ok,degree,Ne(2)
integer :: exc(0:2,2,2)
integer(bit_kind), allocatable :: det_i(:,:)
double precision :: hmono,htwoe,hthree,htilde_ij,accu,phase,normal
double precision :: hmono,htwoe,hthree,htilde_ij,accu,phase,normal,hthree_tmp
integer, allocatable :: occ(:,:)
allocate( occ(N_int*bit_kind_size,2) )
call bitstring_to_list_ab(ref_bitmask, occ, Ne, N_int)
@ -45,15 +45,44 @@ subroutine test
do p1 = elec_alpha_num+1, mo_num
do h2 = 1, elec_beta_num
do p2 = elec_beta_num+1, mo_num
hthree = 0.d0
det_i = ref_bitmask
s1 = 1
s2 = 2
call do_single_excitation(det_i,h1,p1,s1,i_ok)
if(i_ok.ne.1)cycle
call do_single_excitation(det_i,h2,p2,s2,i_ok)
call htilde_mu_mat_bi_ortho_slow(det_i,HF_bitmask,N_int,hmono,htwoe,hthree,htilde_ij)
if(i_ok.ne.1)cycle
call htilde_mu_mat_bi_ortho_slow(det_i,HF_bitmask,N_int,hmono,htwoe,hthree_tmp,htilde_ij)
call get_excitation_degree(ref_bitmask,det_i,degree,N_int)
call get_excitation(ref_bitmask,det_i,exc,degree,phase,N_int)
hthree *= phase
! !normal = normal_two_body_bi_orth_ab(p2,h2,p1,h1)
call three_comp_two_e_elem(det_i,h1,h2,p1,p2,s1,s2,normal)
hthree_tmp *= phase
hthree += 0.5d0 * hthree_tmp
det_i = ref_bitmask
s1 = 2
s2 = 1
call do_single_excitation(det_i,h1,p1,s1,i_ok)
if(i_ok.ne.1)cycle
call do_single_excitation(det_i,h2,p2,s2,i_ok)
if(i_ok.ne.1)cycle
call htilde_mu_mat_bi_ortho_slow(det_i,HF_bitmask,N_int,hmono,htwoe,hthree_tmp,htilde_ij)
call get_excitation_degree(ref_bitmask,det_i,degree,N_int)
call get_excitation(ref_bitmask,det_i,exc,degree,phase,N_int)
hthree_tmp *= phase
hthree += 0.5d0 * hthree_tmp
! normal = normal_two_body_bi_orth_ab(p2,h2,p1,h1)
call give_aba_contraction(N_int, h1, h2, p1, p2, Ne, occ, normal)
if(dabs(hthree).lt.1.d-10)cycle
if(dabs(hthree-normal).gt.1.d-10)then
! print*,pp2,pp1,hh2,hh1
print*,p2,p1,h2,h1
print*,hthree,normal,dabs(hthree-normal)
stop
endif
! call three_comp_two_e_elem(det_i,h1,h2,p1,p2,s1,s2,normal)
! normal = eff_2_e_from_3_e_ab(p2,p1,h2,h1)
accu += dabs(hthree-normal)
enddo
@ -86,8 +115,8 @@ do h1 = 1, elec_alpha_num
integer :: hh1, pp1, hh2, pp2, ss1, ss2
call decode_exc(exc, 2, hh1, pp1, hh2, pp2, ss1, ss2)
hthree *= phase
! normal = normal_two_body_bi_orth_aa_bb(p2,h2,p1,h1)
normal = eff_2_e_from_3_e_aa(p2,p1,h2,h1)
normal = normal_two_body_bi_orth_aa_bb(p2,h2,p1,h1)
! normal = eff_2_e_from_3_e_aa(p2,p1,h2,h1)
if(dabs(hthree).lt.1.d-10)cycle
if(dabs(hthree-normal).gt.1.d-10)then
print*,pp2,pp1,hh2,hh1

9
src/tc_bi_ortho/test_tc_fock.irp.f
View File

@ -152,9 +152,7 @@ subroutine routine_tot()
! do i = 1, elec_num_tab(s1)
! do a = elec_num_tab(s1)+1, mo_num ! virtual
do i = 1, elec_beta_num
do a = elec_beta_num+1, elec_alpha_num! virtual
! do i = elec_beta_num+1, elec_alpha_num
! do a = elec_alpha_num+1, mo_num! virtual
do a = elec_beta_num+1, mo_num! virtual
print*,i,a
det_i = ref_bitmask
@ -167,7 +165,7 @@ subroutine routine_tot()
call htilde_mu_mat_bi_ortho_slow(det_i, ref_bitmask, N_int, hmono, htwoe, hthree, htilde_ij)
print*,htilde_ij
if(dabs(htilde_ij).lt.1.d-10)cycle
! if(dabs(htilde_ij).lt.1.d-10)cycle
print*, ' excited det'
call debug_det(det_i, N_int)
@ -184,9 +182,12 @@ subroutine routine_tot()
! endif
err_ai = dabs(dabs(ref) - dabs(new))
if(err_ai .gt. 1d-7) then
print*,'---------'
print*,'s1 = ',s1
print*, ' warning on', i, a
print*, ref,new,err_ai
print*,hmono, htwoe, hthree
print*,'---------'
endif
print*, ref,new,err_ai
err_tot += err_ai

73
src/tc_bi_ortho/test_tc_two_rdm.irp.f Normal file
View File

@ -0,0 +1,73 @@
program test_tc_rdm
BEGIN_DOC
!
! TODO : Reads psi_det in the EZFIO folder and prints out the left- and right-eigenvectors together
! with the energy. Saves the left-right wave functions at the end.
!
END_DOC
my_grid_becke = .True.
PROVIDE tc_grid1_a tc_grid1_r
my_n_pt_r_grid = tc_grid1_r
my_n_pt_a_grid = tc_grid1_a
touch my_grid_becke my_n_pt_r_grid my_n_pt_a_grid
read_wf = .True.
touch read_wf
print*, ' nb of states = ', N_states
print*, ' nb of det = ', N_det
call test()
end
subroutine test
implicit none
integer :: h1,p1,h2,p2,i,j,istate
double precision :: rdm, integral, accu,ref
double precision :: hmono, htwoe, hthree, htot
accu = 0.d0
do h1 = 1, mo_num
do p1 = 1, mo_num
do h2 = 1, mo_num
do p2 = 1, mo_num
integral = mo_bi_ortho_tc_two_e(p2,p1,h2,h1)
rdm = tc_two_rdm(p1,h1,p2,h2)
! if(dabs(rdm).gt.1.d-10)then
! print*,h1,p1,h2,p2
! print*,rdm,integral,rdm*integral
! endif
accu += integral * rdm
enddo
enddo
enddo
enddo
accu *= 0.5d0
print*,'accu = ',accu
! print*,mo_bi_ortho_tc_two_e(2,15,2,1)
! print*,mo_bi_ortho_tc_two_e(15,2,2,1)
! print*,mo_bi_ortho_tc_two_e(2,1,2,15)
! print*,mo_bi_ortho_tc_two_e(2,1,15,2)
ref = 0.d0
do i = 1, N_det
do j = 1, N_det
! if(i.eq.j)cycle
call htilde_mu_mat_opt_bi_ortho(psi_det(1,1,i), psi_det(1,1,j), N_int, hmono, htwoe, hthree, htot)
do istate = 1,N_states
! print*,'i,j',i,j
! print*,psi_l_coef_bi_ortho(i,istate) , psi_r_coef_bi_ortho(j,istate) , htwoe
! print*,psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,istate) * htwoe
! if(i.ne.j)then
! print*,psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,istate) , htwoe
! print*,psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,istate) * htwoe
! endif
ref += psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,istate) * state_average_weight(istate) * htwoe
enddo
enddo
enddo
print*,' ref = ',ref
print*,'delta= ',ref-accu
end

124
src/tc_bi_ortho/two_rdm_naive.irp.f Normal file
View File

@ -0,0 +1,124 @@
BEGIN_PROVIDER [ double precision, tc_two_rdm, (mo_num, mo_num, mo_num, mo_num)]
implicit none
BEGIN_DOC
! tc_two_rdm(p,s,q,r) = <Phi| a^dager_p
END_DOC
integer :: i,j,istate,m,mm,nn
integer :: exc(0:2,2,2)
double precision :: phase
double precision :: contrib
integer :: h1,p1,s1,h2,p2,s2,degree
integer, allocatable :: occ(:,:)
integer :: n_occ_ab(2),other_spin(2)
other_spin(1) = 2
other_spin(2) = 1
allocate(occ(N_int*bit_kind_size,2))
tc_two_rdm = 0.d0
do i = 1, N_det ! psi_left
do j = 1, N_det ! psi_right
call get_excitation_degree(psi_det(1,1,i),psi_det(1,1,j),degree,N_int)
if(degree.gt.2)cycle
if(degree.gt.0)then
! get excitation operators: from psi_det(j) --> psi_det(i)
call get_excitation(psi_det(1,1,j),psi_det(1,1,i),exc,degree,phase,N_int)
call decode_exc(exc,degree,h1,p1,h2,p2,s1,s2)
contrib = psi_l_coef_bi_ortho(i,1) * psi_r_coef_bi_ortho(j,1) * phase * state_average_weight(1)
do istate = 2, N_states
contrib += psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,istate) * phase * state_average_weight(istate)
enddo
if(degree == 2)then
call update_tc_rdm(h1,p1,h2,p2,s1,s2,tc_two_rdm,mo_num,contrib)
else if(degree==1)then
! occupation of the determinant psi_det(j)
call bitstring_to_list_ab(psi_det(1,1,j), occ, n_occ_ab, N_int)
! run over the electrons of opposite spin than the excitation
s2 = other_spin(s1)
do mm = 1, n_occ_ab(s2)
m = occ(mm,s2)
h2 = m
p2 = m
call update_tc_rdm(h1,p1,h2,p2,s1,s2,tc_two_rdm,mo_num,contrib)
enddo
! run over the electrons of same spin than the excitation
s2 = s1
do mm = 1, n_occ_ab(s2)
m = occ(mm,s2)
h2 = m
p2 = m
call update_tc_rdm(h1,p1,h2,p2,s1,s2,tc_two_rdm,mo_num,contrib)
enddo
endif
else if(degree == 0)then
! cycle
contrib = psi_l_coef_bi_ortho(i,1) * psi_r_coef_bi_ortho(j,1) * state_average_weight(1)
do istate = 2, N_states
contrib += psi_l_coef_bi_ortho(i,istate) * psi_r_coef_bi_ortho(j,istate) * state_average_weight(istate)
enddo
! occupation of the determinant psi_det(j)
call bitstring_to_list_ab(psi_det(1,1,j), occ, n_occ_ab, N_int)
s1 = 1 ! alpha electrons
do nn = 1, n_occ_ab(s1)
h1 = occ(nn,s1)
p1 = occ(nn,s1)
! run over the couple of alpha-beta electrons
s2 = other_spin(s1)
do mm = 1, n_occ_ab(s2)
m = occ(mm,s2)
h2 = m
p2 = m
call update_tc_rdm(h1,p1,h2,p2,s1,s2,tc_two_rdm,mo_num,contrib)
enddo
! run over the couple of alpha-alpha electrons
s2 = s1
do mm = 1, n_occ_ab(s2)
m = occ(mm,s2)
h2 = m
p2 = m
if(h2.le.h1)cycle
call update_tc_rdm(h1,p1,h2,p2,s1,s2,tc_two_rdm,mo_num,contrib)
enddo
enddo
s1 = 2
do nn = 1, n_occ_ab(s1)
h1 = occ(nn,s1)
p1 = occ(nn,s1)
! run over the couple of beta-beta electrons
s2 = s1
do mm = 1, n_occ_ab(s2)
m = occ(mm,s2)
h2 = m
p2 = m
if(h2.le.h1)cycle
call update_tc_rdm(h1,p1,h2,p2,s1,s2,tc_two_rdm,mo_num,contrib)
enddo
enddo
endif
enddo
enddo
END_PROVIDER
subroutine update_tc_rdm(h1,p1,h2,p2,s1,s2,array,sze,contrib)
implicit none
integer, intent(in) :: h1,p1,h2,p2,s1,s2,sze
double precision, intent(in) :: contrib
double precision, intent(inout) :: array(sze, sze, sze, sze)
integer :: istate
if(s1.ne.s2)then
array(p1,h1,p2,h2) += contrib
! permutation for particle symmetry
array(p2,h2,p1,h1) += contrib
else ! same spin double excitation
array(p1,h1,p2,h2) += contrib
! exchange
! exchanging the particles
array(p2,h1,p1,h2) -= contrib
! exchanging the
array(p1,h2,p2,h1) -= contrib
! permutation for particle symmetry
array(p2,h2,p1,h1) += contrib
endif
end

6
src/tc_keywords/EZFIO.cfg
View File

@ -214,6 +214,12 @@ doc: Threshold to determine if diagonal elements of the bi-orthogonal condition
interface: ezfio,provider,ocaml
default: 1.e-6
[thresh_lr_angle]
type: double precision
doc: Maximum value of the angle between the couple of left and right orbital for the rotations
interface: ezfio,provider,ocaml
default: 20.0
[thresh_biorthog_nondiag]
type: Threshold
doc: Threshold to determine if non-diagonal elements of L.T x R are close enouph to 0

24
src/tc_scf/fock_tc.irp.f
View File

@ -208,10 +208,10 @@ BEGIN_PROVIDER [ double precision, Fock_matrix_tc_mo_alpha, (mo_num, mo_num) ]
if(three_body_h_tc) then
!call wall_time(tt0)
!PROVIDE fock_a_tot_3e_bi_orth
!Fock_matrix_tc_mo_alpha += fock_a_tot_3e_bi_orth
PROVIDE fock_3e_uhf_mo_a
Fock_matrix_tc_mo_alpha += fock_3e_uhf_mo_a
PROVIDE fock_a_tot_3e_bi_orth
Fock_matrix_tc_mo_alpha += fock_a_tot_3e_bi_orth
! PROVIDE fock_3e_uhf_mo_a
! Fock_matrix_tc_mo_alpha += fock_3e_uhf_mo_a
!call wall_time(tt1)
!print*, ' 3-e term:', tt1-tt0
endif
@ -241,21 +241,13 @@ BEGIN_PROVIDER [ double precision, Fock_matrix_tc_mo_beta, (mo_num,mo_num) ]
if(bi_ortho) then
!allocate(tmp(ao_num,ao_num))
!tmp = Fock_matrix_tc_ao_beta
!if(three_body_h_tc) then
! tmp += fock_3e_uhf_ao_b
!endif
!call ao_to_mo_bi_ortho(tmp, size(tmp, 1), Fock_matrix_tc_mo_beta, size(Fock_matrix_tc_mo_beta, 1))
!deallocate(tmp)
call ao_to_mo_bi_ortho( Fock_matrix_tc_ao_beta, size(Fock_matrix_tc_ao_beta, 1) &
, Fock_matrix_tc_mo_beta, size(Fock_matrix_tc_mo_beta, 1) )
if(three_body_h_tc) then
!PROVIDE fock_b_tot_3e_bi_orth
!Fock_matrix_tc_mo_beta += fock_b_tot_3e_bi_orth
PROVIDE fock_3e_uhf_mo_b
Fock_matrix_tc_mo_beta += fock_3e_uhf_mo_b
PROVIDE fock_b_tot_3e_bi_orth
Fock_matrix_tc_mo_beta += fock_b_tot_3e_bi_orth
! PROVIDE fock_3e_uhf_mo_b
! Fock_matrix_tc_mo_beta += fock_3e_uhf_mo_b
endif
else

16
src/tc_scf/routines_rotates.irp.f
View File

@ -140,7 +140,11 @@ subroutine routine_save_rotated_mos(thr_deg, good_angles)
! compute the overlap between the left and rescaled right
call build_s_matrix(ao_num, mo_num, mo_r_coef_new, mo_r_coef_new, ao_overlap, s_mat)
! call give_degen(fock_diag,mo_num,thr_deg,list_degen,n_degen_list)
call give_degen_full_list(fock_diag, mo_num, thr_deg, list_degen, n_degen_list)
if(n_core_orb.ne.0)then
call give_degen_full_listcore(fock_diag, mo_num, list_core, n_core_orb, thr_deg, list_degen, n_degen_list)
else
call give_degen_full_list(fock_diag, mo_num, thr_deg, list_degen, n_degen_list)
endif
print *, ' fock_matrix_mo'
do i = 1, mo_num
print *, i, fock_diag(i), angle_left_right(i)
@ -152,6 +156,8 @@ subroutine routine_save_rotated_mos(thr_deg, good_angles)
! n_degen = ilast - ifirst +1
n_degen = list_degen(i,0)
if(n_degen .ge. 1000)n_degen = 1 ! convention for core orbitals
if(n_degen .eq. 1) cycle
allocate(stmp(n_degen,n_degen), smat2(n_degen,n_degen))
@ -279,7 +285,7 @@ subroutine routine_save_rotated_mos(thr_deg, good_angles)
allocate(new_angles(mo_num))
new_angles(1:mo_num) = dabs(angle_left_right(1:mo_num))
max_angle = maxval(new_angles)
good_angles = max_angle.lt.45.d0
good_angles = max_angle.lt.thresh_lr_angle
print *, ' max_angle = ', max_angle
deallocate(new_angles)
@ -397,11 +403,11 @@ subroutine print_energy_and_mos(good_angles)
print *, ' TC SCF energy gradient = ', grad_non_hermit
print *, ' Max angle Left/right = ', max_angle_left_right
if(max_angle_left_right .lt. 45.d0) then
if(max_angle_left_right .lt. thresh_lr_angle) then
print *, ' Maximum angle BELOW 45 degrees, everthing is OK !'
good_angles = .true.
else if(max_angle_left_right .gt. 45.d0 .and. max_angle_left_right .lt. 75.d0) then
print *, ' Maximum angle between 45 and 75 degrees, this is not the best for TC-CI calculations ...'
else if(max_angle_left_right .gt. thresh_lr_angle .and. max_angle_left_right .lt. 75.d0) then
print *, ' Maximum angle between thresh_lr_angle and 75 degrees, this is not the best for TC-CI calculations ...'
good_angles = .false.
else if(max_angle_left_right .gt. 75.d0) then
print *, ' Maximum angle between ABOVE 75 degrees, YOU WILL CERTAINLY FIND TROUBLES IN TC-CI calculations ...'

244
src/utils/block_diag_degen_core.irp.f Normal file
View File

@ -0,0 +1,244 @@
subroutine diag_mat_per_fock_degen_core(fock_diag, mat_ref, listcore,ncore, n, thr_d, thr_nd, thr_deg, leigvec, reigvec, eigval)
BEGIN_DOC
!
! subroutine that diagonalizes a matrix mat_ref BY BLOCK
!
! the blocks are defined by the elements having the SAME DEGENERACIES in the entries "fock_diag"
!
! the elements of listcore are untouched
!
! examples : all elements having degeneracy 1 in fock_diag (i.e. not being degenerated) will be treated together
!
! : all elements having degeneracy 2 in fock_diag (i.e. two elements are equal) will be treated together
!
! : all elements having degeneracy 3 in fock_diag (i.e. two elements are equal) will be treated together
!
! etc... the advantage is to guarentee no spurious mixing because of numerical problems.
!
END_DOC
implicit none
integer, intent(in) :: n,ncore, listcore(ncore)
double precision, intent(in) :: fock_diag(n), mat_ref(n,n), thr_d, thr_nd, thr_deg
double precision, intent(out) :: leigvec(n,n), reigvec(n,n), eigval(n)
integer :: n_degen_list, n_degen,size_mat, i, j, k, icount, m, index_degen
integer :: ii, jj, i_good, j_good, n_real
integer :: icount_eigval
logical, allocatable :: is_ok(:)
integer, allocatable :: list_degen(:,:), list_same_degen(:)
integer, allocatable :: iorder(:), list_degen_sorted(:)
double precision, allocatable :: leigvec_unsrtd(:,:), reigvec_unsrtd(:,:), eigval_unsrtd(:)
double precision, allocatable :: mat_tmp(:,:), eigval_tmp(:), leigvec_tmp(:,:), reigvec_tmp(:,:)
allocate(leigvec_unsrtd(n,n), reigvec_unsrtd(n,n), eigval_unsrtd(n))
leigvec_unsrtd = 0.d0
reigvec_unsrtd = 0.d0
eigval_unsrtd = 0.d0
! obtain degeneracies
allocate(list_degen(n,0:n))
call give_degen_full_listcore(fock_diag, n, listcore, ncore, thr_deg, list_degen, n_degen_list)
allocate(iorder(n_degen_list), list_degen_sorted(n_degen_list))
do i = 1, n_degen_list
n_degen = list_degen(i,0)
list_degen_sorted(i) = n_degen
iorder(i) = i
enddo
! sort by number of degeneracies
call isort(list_degen_sorted, iorder, n_degen_list)
allocate(is_ok(n_degen_list))
is_ok = .True.
icount_eigval = 0
! loop over degeneracies
do i = 1, n_degen_list
if(.not.is_ok(i)) cycle
is_ok(i) = .False.
n_degen = list_degen_sorted(i)
if(n_degen.ge.1000)then
print*,'core orbital '
else
print *, ' diagonalizing for n_degen = ', n_degen
endif
k = 1
! group all the entries having the same degeneracies
!! do while (list_degen_sorted(i+k)==n_degen)
do m = i+1, n_degen_list
if(list_degen_sorted(m)==n_degen) then
is_ok(i+k) = .False.
k += 1
endif
enddo
print *, ' number of identical degeneracies = ', k
if(n_degen.ge.1000)then
n_degen = 1
endif
size_mat = k*n_degen
print *, ' size_mat = ', size_mat
allocate(mat_tmp(size_mat,size_mat), list_same_degen(size_mat))
allocate(eigval_tmp(size_mat), leigvec_tmp(size_mat,size_mat), reigvec_tmp(size_mat,size_mat))
! group all the elements sharing the same degeneracy
icount = 0
do j = 1, k ! jth set of degeneracy
index_degen = iorder(i+j-1)
do m = 1, n_degen
icount += 1
list_same_degen(icount) = list_degen(index_degen,m)
enddo
enddo
print *, ' list of elements '
do icount = 1, size_mat
print *, icount, list_same_degen(icount)
enddo
! you copy subset of matrix elements having all the same degeneracy in mat_tmp
do ii = 1, size_mat
i_good = list_same_degen(ii)
do jj = 1, size_mat
j_good = list_same_degen(jj)
mat_tmp(jj,ii) = mat_ref(j_good,i_good)
enddo
enddo
call non_hrmt_bieig( size_mat, mat_tmp, thr_d, thr_nd &
, leigvec_tmp, reigvec_tmp &
, n_real, eigval_tmp )
do ii = 1, size_mat
icount_eigval += 1
eigval_unsrtd(icount_eigval) = eigval_tmp(ii) ! copy eigenvalues
do jj = 1, size_mat ! copy the eigenvectors
j_good = list_same_degen(jj)
leigvec_unsrtd(j_good,icount_eigval) = leigvec_tmp(jj,ii)
reigvec_unsrtd(j_good,icount_eigval) = reigvec_tmp(jj,ii)
enddo
enddo
deallocate(mat_tmp, list_same_degen)
deallocate(eigval_tmp, leigvec_tmp, reigvec_tmp)
enddo
if(icount_eigval .ne. n) then
print *, ' pb !! (icount_eigval.ne.n)'
print *, ' icount_eigval,n', icount_eigval, n
stop
endif
deallocate(iorder)
allocate(iorder(n))
do i = 1, n
iorder(i) = i
enddo
call dsort(eigval_unsrtd, iorder, n)
do i = 1, n
print*,'sorted eigenvalues '
i_good = iorder(i)
eigval(i) = eigval_unsrtd(i)
print*,'i,eigval(i) = ',i,eigval(i)
do j = 1, n
leigvec(j,i) = leigvec_unsrtd(j,i_good)
reigvec(j,i) = reigvec_unsrtd(j,i_good)
enddo
enddo
deallocate(leigvec_unsrtd, reigvec_unsrtd, eigval_unsrtd)
deallocate(list_degen)
deallocate(iorder, list_degen_sorted)
deallocate(is_ok)
end
! ---
subroutine give_degen_full_listcore(A, n, listcore, ncore, thr, list_degen, n_degen_list)
BEGIN_DOC
! you enter with an array A(n) and spits out all the elements degenerated up to thr
!
! the elements of A(n) DON'T HAVE TO BE SORTED IN THE ENTRANCE: TOTALLY GENERAL
!
! list_degen(i,0) = number of degenerate entries
!
! list_degen(i,1) = index of the first degenerate entry
!
! list_degen(i,2:list_degen(i,0)) = list of all other dengenerate entries
!
! if list_degen(i,0) == 1 it means that there is no degeneracy for that element
!
! if list_degen(i,0) >= 1000 it means that it is core orbitals
END_DOC
implicit none
double precision, intent(in) :: A(n)
double precision, intent(in) :: thr
integer, intent(in) :: n,ncore, listcore(ncore)
integer, intent(out) :: list_degen(n,0:n), n_degen_list
integer :: i, j, icount, icheck,k
logical, allocatable :: is_ok(:)
allocate(is_ok(n))
n_degen_list = 0
is_ok = .True.
! you first exclude the "core" orbitals
do i = 1, ncore
j=listcore(i)
is_ok(j) = .False.
enddo
do i = 1, n
if(.not.is_ok(i)) cycle
n_degen_list +=1
is_ok(i) = .False.
list_degen(n_degen_list,1) = i
icount = 1
do j = i+1, n
if(dabs(A(i)-A(j)).lt.thr.and.is_ok(j)) then
is_ok(j) = .False.
icount += 1
list_degen(n_degen_list,icount) = j
endif
enddo
list_degen(n_degen_list,0) = icount
enddo
! you set all the core orbitals as separate entities
icheck = 0
do i = 1, n_degen_list
icheck += list_degen(i,0)
enddo
if(icheck.ne.(n-ncore))then
print *, ' pb ! :: icheck.ne.n-ncore'
print *, icheck, n-ncore
stop
endif
k=1000
do i = 1, ncore
n_degen_list+= 1
j=listcore(i)
list_degen(n_degen_list,1) = i
list_degen(n_degen_list,0) = k
k+=1
enddo
end
! ---

1
src/utils/fortran_mmap.c
View File

@ -9,7 +9,6 @@
void* mmap_fortran(char* filename, size_t bytes, int* file_descr, int read_only)
{
int i;
int fd;
int result;
void* map;

10
src/utils/linear_algebra.irp.f
View File

@ -1661,7 +1661,15 @@ subroutine restore_symmetry(m,n,A,LDA,thresh)
! Update i
i = i + 1
enddo
copy(i:) = 0.d0
! To nullify the remaining elements that are below the threshold
if (i == sze) then
if (-copy(i) <= thresh) then
copy(i) = 0d0
endif
else
copy(i:) = 0.d0
endif
!$OMP PARALLEL if (sze>10000) &
!$OMP SHARED(m,sze,copy_sign,copy,key,A,ii,jj) &