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working on casscf_cipsi

This commit is contained in:
eginer 2023-10-06 11:28:20 +02:00
parent dbd0f16307
commit 2b62bfc999
8 changed files with 153 additions and 27 deletions
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6
src/casscf_cipsi/EZFIO.cfg
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@ -73,3 +73,9 @@ 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
[small_active_space]
type: logical
doc: If |true|, the pt2_max value in the CIPSI is set to 10-10 and will not change
interface: ezfio,provider,ocaml
default: False

36
src/casscf_cipsi/README.rst
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@ -3,3 +3,39 @@ casscf
======
|CASSCF| program with the CIPSI algorithm.
Example of inputs
-----------------
a) Small active space : standard CASSCF
---------------------------------------
Let's do O2 (triplet) in aug-cc-pvdz with the following geometry (xyz format, Bohr units)
3
O 0.0000000000 0.0000000000 -1.1408000000
O 0.0000000000 0.0000000000 1.1408000000
# Create the ezfio folder
qp create_ezfio -b aug-cc-pvdz O2.xyz -m 3 -a -o O2_avdz
# Start with an ROHF guess
qp run scf | tee ${EZFIO_FILE}.rohf.out
# Get the ROHF energy for check
qp get hartree_fock energy # should be -149.4684509
# Define the full valence active space: the two 1s are doubly occupied, the other 8 valence orbitals are active
# CASSCF(12e,10orb)
qp set_mo_class -c "[1-2]" -a "[3-10]" -v "[11-46]"
# Specify that you want an near exact CASSCF, i.e. the CIPSI selection will stop at pt2_max = 10^-10
qp set casscf_cipsi small_active_space True
# RUN THE CASSCF
qp run casscf | tee ${EZFIO_FILE}.casscf.out
b) Large active space : Exploit the selected CI in the active space
-------------------------------------------------------------------
Let us start from the small active space calculation orbitals and add another shell of

83
src/casscf_cipsi/casscf.irp.f
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@ -8,17 +8,22 @@ program casscf
! touch no_vvvv_integrals
n_det_max_full = 500
touch n_det_max_full
pt2_relative_error = 0.04
if(small_active_space)then
pt2_relative_error = 0.00001
else
pt2_relative_error = 0.04
endif
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
double precision :: energy_old, energy, pt2_max_before,delta_E
logical :: converged,state_following_casscf_cipsi_save
integer :: iteration
integer :: iteration,istate
double precision, allocatable :: E_PT2(:), PT2(:), Ev(:), ept2_before(:)
allocate(E_PT2(N_states), PT2(N_states), Ev(N_states), ept2_before(N_states))
converged = .False.
energy = 0.d0
@ -28,13 +33,19 @@ subroutine run
state_following_casscf = .True.
touch state_following_casscf
ept2_before = 0.d0
if(adaptive_pt2_max)then
pt2_max = 0.005
if(small_active_space)then
pt2_max = 1.d-10
SOFT_TOUCH pt2_max
else
if(adaptive_pt2_max)then
pt2_max = 0.005
SOFT_TOUCH pt2_max
endif
endif
do while (.not.converged)
print*,'pt2_max = ',pt2_max
call run_stochastic_cipsi
call run_stochastic_cipsi(Ev,PT2)
E_PT2(1:N_states) = Ev(1:N_states) + PT2(1:N_states)
energy_old = energy
energy = eone+etwo+ecore
pt2_max_before = pt2_max
@ -42,15 +53,13 @@ subroutine run
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 = ')
! if(n_states == 1)then
! call ezfio_get_casscf_cipsi_energy_pt2(E_PT2)
! call ezfio_get_casscf_cipsi_energy(PT2)
call write_double(6,E_PT2(1:N_states),'E + PT2 energy = ')
call write_double(6,PT2(1:N_states),' PT2 = ')
call write_double(6,pt2_max,' PT2_MAX = ')
endif
! endif
print*,''
call write_double(6,norm_grad_vec2,'Norm of gradients = ')
@ -65,15 +74,20 @@ subroutine run
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)
delta_E = 0.d0
do istate = 1, N_states
delta_E += dabs(E_PT2(istate) - ept2_before(istate))
enddo
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)
if(.not.small_active_space)then
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
endif
print*,''
@ -94,8 +108,10 @@ subroutine run
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
if(.not.small_active_space)then
if(adaptive_pt2_max)then
SOFT_TOUCH pt2_max
endif
endif
if(iteration .gt. 3)then
state_following_casscf = state_following_casscf_cipsi_save
@ -104,6 +120,27 @@ subroutine run
endif
enddo
integer :: i
! print*,'Converged CASSCF '
! print*,'--------------------------'
! write(6,*) ' occupation numbers of orbitals '
! do i=1,mo_num
! write(6,*) i,occnum(i)
! end do
!
! 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,*)
print*,'Fock ROHF '
do i = 1, ao_num
write(33,*)fock_matrix_ao_alpha(i,1:ao_num)
enddo
print*,'Fock MCSCF'
do i = 1, ao_num
write(34,*)mcscf_fock_alpha(i,1:ao_num)
enddo
end

29
src/casscf_cipsi/densities.irp.f
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@ -17,6 +17,35 @@ BEGIN_PROVIDER [real*8, D0tu, (n_act_orb,n_act_orb) ]
END_PROVIDER
BEGIN_PROVIDER [double precision, D0tu_alpha_ao, (ao_num, ao_num)]
&BEGIN_PROVIDER [double precision, D0tu_beta_ao, (ao_num, ao_num)]
implicit none
integer :: i,ii,j,u,t,uu,tt
double precision, allocatable :: D0_tmp_alpha(:,:),D0_tmp_beta(:,:)
allocate(D0_tmp_alpha(mo_num, mo_num),D0_tmp_beta(mo_num, mo_num))
D0_tmp_beta = 0.d0
D0_tmp_alpha = 0.d0
do i = 1, n_core_inact_orb
ii = list_core_inact(i)
D0_tmp_alpha(ii,ii) = 1.d0
D0_tmp_beta(ii,ii) = 1.d0
enddo
print*,'Diagonal elements of the 1RDM in the active space'
do u=1,n_act_orb
uu = list_act(u)
print*,uu,one_e_dm_mo_alpha_average(uu,uu),one_e_dm_mo_beta_average(uu,uu)
do t=1,n_act_orb
tt = list_act(t)
D0_tmp_alpha(tt,uu) = one_e_dm_mo_alpha_average(tt,uu)
D0_tmp_beta(tt,uu) = one_e_dm_mo_beta_average(tt,uu)
enddo
enddo
call mo_to_ao_no_overlap(D0_tmp_alpha,mo_num,D0tu_alpha_ao,ao_num)
call mo_to_ao_no_overlap(D0_tmp_beta,mo_num,D0tu_beta_ao,ao_num)
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

13
src/casscf_cipsi/mcscf_fock.irp.f
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@ -77,4 +77,15 @@ BEGIN_PROVIDER [real*8, Fapq, (mo_num,mo_num) ]
END_PROVIDER
BEGIN_PROVIDER [ double precision, mcscf_fock_alpha, (ao_num, ao_num)]
&BEGIN_PROVIDER [ double precision, mcscf_fock_beta, (ao_num, ao_num)]
implicit none
BEGIN_DOC
! mcscf_fock_alpha are set to usual Fock like operator but computed with the MCSCF densities
END_DOC
SCF_density_matrix_ao_alpha = D0tu_alpha_ao
SCF_density_matrix_ao_beta = D0tu_beta_ao
soft_touch SCF_density_matrix_ao_alpha SCF_density_matrix_ao_beta
mcscf_fock_beta = fock_matrix_ao_beta
mcscf_fock_alpha = fock_matrix_ao_alpha
END_PROVIDER

5
src/cipsi/stochastic_cipsi.irp.f
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@ -1,10 +1,11 @@
subroutine run_stochastic_cipsi
subroutine run_stochastic_cipsi(Ev,PT2)
use selection_types
implicit none
BEGIN_DOC
! Selected Full Configuration Interaction with Stochastic selection and PT2.
END_DOC
integer :: i,j,k
double precision, intent(out) :: Ev(N_states), PT2(N_states)
double precision, allocatable :: zeros(:)
integer :: to_select
type(pt2_type) :: pt2_data, pt2_data_err
@ -139,6 +140,8 @@ subroutine run_stochastic_cipsi
call print_mol_properties()
call write_cipsi_json(pt2_data,pt2_data_err)
endif
Ev(1:N_states) = psi_energy_with_nucl_rep(1:N_states)
PT2(1:N_states) = pt2_data % pt2(1:N_states)
call pt2_dealloc(pt2_data)
call pt2_dealloc(pt2_data_err)

4
src/fci/fci.irp.f
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@ -41,8 +41,10 @@ program fci
write(json_unit,json_array_open_fmt) 'fci'
double precision, allocatable :: Ev(:),PT2(:)
allocate(Ev(N_states), PT2(N_state))
if (do_pt2) then
call run_stochastic_cipsi
call run_stochastic_cipsi(Ev,PT2)
else
call run_cipsi
endif

4
src/mo_optimization/cipsi_orb_opt.irp.f
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@ -11,11 +11,13 @@ subroutine run_optimization
implicit none
double precision :: e_cipsi, e_opt, delta_e
double precision, allocatable :: Ev(:),PT2(:)
integer :: nb_iter,i
logical :: not_converged
character (len=100) :: filename
PROVIDE psi_det psi_coef mo_two_e_integrals_in_map ao_pseudo_integrals
allocate(Ev(N_states),PT2(N_states))
not_converged = .True.
nb_iter = 0
@ -38,7 +40,7 @@ subroutine run_optimization
print*,''
print*,'********** cipsi step **********'
! cispi calculation
call run_stochastic_cipsi
call run_stochastic_cipsi(Ev,PT2)
! State average energy after the cipsi step
call state_average_energy(e_cipsi)