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quantum_package/plugins/OVB/ovb_components.irp.f
2016-02-17 10:52:57 +01:00

511 lines
19 KiB
Fortran

use bitmasks
BEGIN_PROVIDER [integer, max_number_ionic]
&BEGIN_PROVIDER [integer, min_number_ionic]
BEGIN_DOC
! Maximum and minimum number of ionization in psi_ref
END_DOC
implicit none
integer :: i,j
integer :: n_closed_shell_cas
max_number_ionic = 0
min_number_ionic = 100000
do i = 1, N_det_ref
j = n_closed_shell_cas(psi_ref(1,1,i),n_int)
if(j> max_number_ionic)then
max_number_ionic = j
endif
if(j< min_number_ionic)then
min_number_ionic = j
endif
enddo
print*,'max_number_ionic = ',max_number_ionic
print*,'min_number_ionic = ',min_number_ionic
END_PROVIDER
BEGIN_PROVIDER [integer, ionic_index, (min_number_ionic:max_number_ionic,0:N_det_ref)]
&BEGIN_PROVIDER [double precision, normalization_factor_ionic, (min_number_ionic:max_number_ionic, N_states)]
BEGIN_DOC
! Index of the various determinants in psi_ref according to their level of ionicity
! ionic_index(i,0) = number of determinants in psi_ref having the degree of ionicity "i"
! ionic_index(i,j) = index of the determinants having the degree of ionicity "i"
END_DOC
implicit none
integer :: i,j,k
integer :: n_closed_shell_cas
double precision :: accu
ionic_index = 0
do i = 1, N_det_ref
j = n_closed_shell_cas(psi_ref(1,1,i),n_int)
ionic_index(j,0) +=1
ionic_index(j,ionic_index(j,0)) = i
enddo
do i = min_number_ionic,max_number_ionic
accu = 0.d0
do j = 1, N_states
do k = 1, ionic_index(i,0)
accu += psi_ref_coef_diagonalized(ionic_index(i,k),j) * psi_ref_coef_diagonalized(ionic_index(i,k),j)
enddo
normalization_factor_ionic(i,j) = 1.d0/dsqrt(accu)
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [double precision, H_OVB_naked, (min_number_ionic:max_number_ionic, min_number_ionic:max_number_ionic, n_states)]
BEGIN_DOC
! Hamiltonian matrix expressed in the basis of contracted forms in terms of ionic structures
END_DOC
implicit none
integer :: i,j,istate,k,l
double precision :: accu,hij
do i = min_number_ionic,max_number_ionic
do j = min_number_ionic,max_number_ionic
do istate = 1, N_states
accu = 0.d0
do k = 1, ionic_index(i,0)
do l = 1, ionic_index(j,0)
hij = ref_hamiltonian_matrix(ionic_index(i,k),ionic_index(j,l))
accu += psi_ref_coef_diagonalized(ionic_index(i,k),istate) * normalization_factor_ionic(i,istate) * &
psi_ref_coef_diagonalized(ionic_index(j,l),istate) * normalization_factor_ionic(j,istate) * hij
enddo
enddo
H_OVB_naked(i,j,istate) = accu
enddo
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [integer, n_couples_act_orb]
implicit none
n_couples_act_orb = 3
END_PROVIDER
BEGIN_PROVIDER [integer, couples_act_orb, (n_couples_act_orb,2) ]
implicit none
couples_act_orb(1,1) = 20
couples_act_orb(1,2) = 21
couples_act_orb(2,1) = 22
couples_act_orb(2,2) = 23
couples_act_orb(3,1) = 24
couples_act_orb(3,2) = 25
END_PROVIDER
BEGIN_PROVIDER [double precision, H_matrix_between_ionic_on_given_atom , (n_act_orb,n_act_orb)]
implicit none
BEGIN_DOC
! Hamiltonian matrix elements between the various contracted functions
! that have a negative charge on a given active orbital
END_DOC
integer :: i,j,k,l,jj,ii
integer(bit_kind), allocatable :: key_1(:,:),key_2(:,:)
double precision :: accu,hij
double precision :: norm
allocate (key_1(N_int,2),key_2(N_int,2))
do i = 1, n_act_orb
j = i ! Diagonal part
norm = 0.d0
accu = 0.d0
do k = 1, n_det_ionic_on_given_atom(i)
norm += psi_coef_mono_ionic_on_given_atom(k,i) **2
do ii = 1, N_int
key_1(ii,1) = psi_det_mono_ionic_on_given_atom(ii,1,k,i)
key_1(ii,2) = psi_det_mono_ionic_on_given_atom(ii,2,k,i)
enddo
do l = 1, n_det_ionic_on_given_atom(j)
do jj = 1, N_int
key_2(jj,1) = psi_det_mono_ionic_on_given_atom(jj,1,l,j)
key_2(jj,2) = psi_det_mono_ionic_on_given_atom(jj,2,l,j)
enddo
call i_H_j(key_1,key_2,N_int,hij)
accu += psi_coef_mono_ionic_on_given_atom(l,j) * psi_coef_mono_ionic_on_given_atom(k,i) * hij
enddo
enddo
H_matrix_between_ionic_on_given_atom(i,j) = accu
do j = i+1, n_act_orb ! Extra diagonal part
accu = 0.d0
do k = 1, n_det_ionic_on_given_atom(i)
do jj = 1, N_int
key_1(jj,1) = psi_det_mono_ionic_on_given_atom(jj,1,k,i)
key_1(jj,2) = psi_det_mono_ionic_on_given_atom(jj,2,k,i)
enddo
do l = 1, n_det_ionic_on_given_atom(j)
do jj = 1, N_int
key_2(jj,1) = psi_det_mono_ionic_on_given_atom(jj,1,l,j)
key_2(jj,2) = psi_det_mono_ionic_on_given_atom(jj,2,l,j)
enddo
call i_H_j(key_1,key_2,N_int,hij)
accu += psi_coef_mono_ionic_on_given_atom(l,j) * psi_coef_mono_ionic_on_given_atom(k,i) * hij
enddo
enddo
H_matrix_between_ionic_on_given_atom(i,j) = accu
H_matrix_between_ionic_on_given_atom(j,i) = accu
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [double precision, H_matrix_between_ionic_on_given_atom_and_others , (n_act_orb,min_number_ionic:max_number_ionic)]
implicit none
use bitmasks
BEGIN_DOC
! Hamiltonian matrix elements between the various contracted functions
! that have a negative charge on a given active orbital
! and all the other fully contracted OVB structures
END_DOC
integer :: i,j,k,l,jj,ii
integer(bit_kind), allocatable :: key_1(:,:),key_2(:,:)
double precision :: accu,hij
double precision :: norm
allocate (key_1(N_int,2),key_2(N_int,2))
do i = 1, n_act_orb
do j = min_number_ionic,max_number_ionic
if(j==1)then
H_matrix_between_ionic_on_given_atom_and_others(i,j) = 0.d0
endif
accu = 0.d0
do k = 1, n_det_ionic_on_given_atom(i)
do jj = 1, N_int
key_1(jj,1) = psi_det_mono_ionic_on_given_atom(jj,1,k,i)
key_1(jj,2) = psi_det_mono_ionic_on_given_atom(jj,2,k,i)
enddo
do l = 1, ionic_index(j,0)
do ii = 1, N_int
key_2(ii,1) = psi_det_ovb(ii,1,l,j)
key_2(ii,2) = psi_det_ovb(ii,2,l,j)
enddo
call i_H_j(key_1,key_2,N_int,hij)
accu += psi_coef_ovb(l,j) * psi_coef_mono_ionic_on_given_atom(k,i) * hij
enddo
enddo
H_matrix_between_ionic_on_given_atom_and_others(i,j) = accu
enddo
enddo
print*,'H_matrix_between_ionic_on_given_atom_and_others'
print*,''
do i = 1, n_act_orb
write(*,'(I3,X,100(F16.7))'),H_matrix_between_ionic_on_given_atom_and_others(i,:)
enddo
END_PROVIDER
BEGIN_PROVIDER [integer, n_det_ionic_on_given_atom, (n_act_orb)]
&BEGIN_PROVIDER [double precision, normalization_factor_ionic_on_given_atom, (n_act_orb) ]
&BEGIN_PROVIDER [double precision, psi_coef_mono_ionic_on_given_atom, (N_det_ref,n_act_orb) ]
&BEGIN_PROVIDER [integer(bit_kind), psi_det_mono_ionic_on_given_atom, (N_int,2,N_det_ref,n_act_orb)]
implicit none
use bitmasks
BEGIN_DOC
! number of determinants that are mono ionic with the negative charge
! on a given atom, normalization_factor, array of determinants,and coefficients
END_DOC
integer :: i,j,k,l
ionicity_level = 1
integer :: ionicity_level
logical :: doubly_occupied_array(n_act_orb)
n_det_ionic_on_given_atom = 0
normalization_factor_ionic_on_given_atom = 0.d0
do i = 1, ionic_index(ionicity_level,0)
call give_index_of_doubly_occ_in_active_space(psi_det(1,1,ionic_index(ionicity_level,i)),doubly_occupied_array)
do j = 1, n_act_orb
if(doubly_occupied_array(j))then
n_det_ionic_on_given_atom(j) += 1
normalization_factor_ionic_on_given_atom(j) += psi_ref_coef_diagonalized(ionic_index(1,i),1) **2
do k = 1, N_int
psi_det_mono_ionic_on_given_atom(k,1,n_det_ionic_on_given_atom(j),j) = psi_det(k,1,ionic_index(ionicity_level,i))
psi_det_mono_ionic_on_given_atom(k,2,n_det_ionic_on_given_atom(j),j) = psi_det(k,2,ionic_index(ionicity_level,i))
enddo
psi_coef_mono_ionic_on_given_atom(n_det_ionic_on_given_atom(j),j) = psi_ref_coef_diagonalized(ionic_index(1,i),1)
endif
enddo
enddo
integer :: i_count
i_count = 0
do j = 1, n_act_orb
i_count += n_det_ionic_on_given_atom(j)
normalization_factor_ionic_on_given_atom(j) = 1.d0/dsqrt(normalization_factor_ionic_on_given_atom(j))
enddo
if(i_count.ne.ionic_index(ionicity_level,0))then
print*,'PB with n_det_ionic_on_given_atom'
print*,'i_count = ',i_count
print*,'ionic_index(ionicity_level,0)',ionic_index(ionicity_level,0)
stop
endif
do j = 1, n_act_orb
do i = 1, n_det_ionic_on_given_atom(j)
psi_coef_mono_ionic_on_given_atom(i,j) = psi_coef_mono_ionic_on_given_atom(i,j) * normalization_factor_ionic_on_given_atom(j)
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [integer(bit_kind), psi_det_ovb, (N_int,2,N_det_ref,min_number_ionic:max_number_ionic)]
&BEGIN_PROVIDER [double precision, psi_coef_ovb, (N_det_ref,min_number_ionic:max_number_ionic) ]
implicit none
BEGIN_DOC
! Array of the determinants belonging to each ovb structures (neutral, mono ionic, bi ionic etc ...)
! together with the arrays of coefficients
END_DOC
integer :: i,j,k,l
use bitmasks
integer :: ionicity_level,i_count
double precision :: accu
do ionicity_level = min_number_ionic,max_number_ionic
accu = 0.d0
do i = 1, ionic_index(ionicity_level,0)
do j = 1, N_int
psi_det_ovb(j,1,i,ionicity_level) = psi_det(j,1,ionic_index(ionicity_level,i))
psi_det_ovb(j,2,i,ionicity_level) = psi_det(j,2,ionic_index(ionicity_level,i))
enddo
psi_coef_ovb(i,ionicity_level) = psi_ref_coef_diagonalized(ionic_index(ionicity_level,i),1) * normalization_factor_ionic(ionicity_level,1)
accu += psi_coef_ovb(i,ionicity_level)**2
enddo
accu = 1.d0/dsqrt(accu)
do i = 1, ionic_index(ionicity_level,0)
psi_coef_ovb(i,ionicity_level) = psi_coef_ovb(i,ionicity_level) * accu
enddo
accu = 0.d0
do i = 1, ionic_index(ionicity_level,0)
accu += psi_coef_ovb(i,ionicity_level) **2
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [double precision, H_matrix_psi_det_ovb, (min_number_ionic:max_number_ionic,min_number_ionic:max_number_ionic)]
implicit none
BEGIN_DOC
! H matrix between the fully contracted OVB forms
END_DOC
integer :: i,j,k,l,jj,ii
integer(bit_kind), allocatable :: key_1(:,:),key_2(:,:)
use bitmasks
double precision :: accu,hij
double precision :: norm
allocate (key_1(N_int,2),key_2(N_int,2))
do i = min_number_ionic,max_number_ionic
do j = min_number_ionic,max_number_ionic
accu = 0.d0
do k = 1, ionic_index(i,0)
do ii = 1, N_int
key_1(ii,1) = psi_det_ovb(ii,1,k,i)
key_1(ii,2) = psi_det_ovb(ii,2,k,i)
enddo
do l = 1, ionic_index(j,0)
do ii = 1, N_int
key_2(ii,1) = psi_det_ovb(ii,1,l,j)
key_2(ii,2) = psi_det_ovb(ii,2,l,j)
enddo
call i_H_j(key_1,key_2,N_int,hij)
accu += psi_coef_ovb(l,j) * psi_coef_ovb(k,i) * hij
enddo
enddo
H_matrix_psi_det_ovb(i,j) = accu
enddo
enddo
END_PROVIDER
BEGIN_PROVIDER [integer, number_first_ionic_couples]
&BEGIN_PROVIDER [logical , is_a_first_ionic_couple, (N_det_ref)]
&BEGIN_PROVIDER [double precision, normalization_factor_special_first_ionic, (2)]
implicit none
BEGIN_DOC
! Number of determinants belonging to the class of first ionic
! AND that have a couple of positive/negative charge belonging
! to a couple of orbital couples_act_orb
! If is_a_first_ionic_couple(i) = .True. then this determinant is a first ionic
! and have a couple of positive/negative charge belonging
! to a couple of orbital couples_act_orb
! normalization factor (1) = 1/(sum c_i^2 .with. is_a_first_ionic_couple(i) = .True.)
! normalization factor (2) = 1/(sum c_i^2 .with. is_a_first_ionic_couple(i) = .False.)
END_DOC
integer :: i,j
use bitmasks
number_first_ionic_couples = 0
integer :: ionicity_level
logical :: couples_out(0:n_couples_act_orb)
integer(bit_kind) :: key_tmp(N_int,2)
ionicity_level = 1
normalization_factor_special_first_ionic = 0.d0
do i = 1, ionic_index(ionicity_level,0)
do j = 1, N_int
key_tmp(j,1) = psi_det(j,1,ionic_index(ionicity_level,i))
key_tmp(j,2) = psi_det(j,2,ionic_index(ionicity_level,i))
enddo
call doubly_occ_empty_in_couple(key_tmp,n_couples_act_orb,couples_act_orb,couples_out)
if(couples_out(0))then
number_first_ionic_couples +=1
is_a_first_ionic_couple(i) = .True.
normalization_factor_special_first_ionic(1) += psi_ref_coef_diagonalized(ionic_index(1,i),1) **2
else
is_a_first_ionic_couple(i) = .False.
normalization_factor_special_first_ionic(2) += psi_ref_coef_diagonalized(ionic_index(1,i),1) **2
endif
enddo
normalization_factor_special_first_ionic(1) = 1.d0/dsqrt(normalization_factor_special_first_ionic(1))
normalization_factor_special_first_ionic(2) = 1.d0/dsqrt(normalization_factor_special_first_ionic(2))
print*,'number_first_ionic_couples = ',number_first_ionic_couples
END_PROVIDER
BEGIN_PROVIDER [integer, number_neutral_no_hund_couples]
&BEGIN_PROVIDER [logical , is_a_neutral_no_hund_couple, (N_det_ref)]
&BEGIN_PROVIDER [double precision, normalization_factor_neutra_no_hund_couple, (2)]
&BEGIN_PROVIDER [double precision, ratio_hund_no_hund ]
implicit none
BEGIN_DOC
! Number of determinants belonging to the class of neutral determinants
! AND that have a couple of alpha beta electrons in couple of orbital couples_act_orb
! If is_a_neutral_no_hund_couple(i) = .True. then this determinant is a neutral determinants
! and have a a couple of alpha beta electrons in couple of orbital couples_act_orb
! normalization factor (1) = 1/sqrt(sum c_i^2 .with. is_a_neutral_no_hund_couple(i) = .True.)
! normalization factor (2) = 1/sqrt(sum c_i^2 .with. is_a_neutral_no_hund_couple(i) = .False.)
END_DOC
integer :: i,j
use bitmasks
number_neutral_no_hund_couples = 0
integer :: ionicity_level
logical :: couples_out(0:n_couples_act_orb)
integer(bit_kind) :: key_tmp(N_int,2)
integer :: ifirst_hund,ifirst_no_hund
double precision :: coef_ref_hund,coef_ref_no_hund
ifirst_hund = 0
ifirst_no_hund = 0
ionicity_level = 0
normalization_factor_neutra_no_hund_couple = 0.d0
do i = 1, ionic_index(ionicity_level,0)
do j = 1, N_int
key_tmp(j,1) = psi_det(j,1,ionic_index(ionicity_level,i))
key_tmp(j,2) = psi_det(j,2,ionic_index(ionicity_level,i))
enddo
call neutral_no_hund_in_couple(key_tmp,n_couples_act_orb,couples_act_orb,couples_out)
if(couples_out(0))then
if(ifirst_no_hund == 0)then
coef_ref_no_hund = psi_ref_coef_diagonalized(ionic_index(ionicity_level,i),1)
ifirst_no_hund = 1
endif
number_neutral_no_hund_couples +=1
is_a_neutral_no_hund_couple(i) = .True.
normalization_factor_neutra_no_hund_couple(1) += psi_ref_coef_diagonalized(ionic_index(ionicity_level,i),1) **2
else
if(ifirst_hund == 0)then
coef_ref_hund = psi_ref_coef_diagonalized(ionic_index(ionicity_level,i),1)
ifirst_hund = 1
endif
is_a_neutral_no_hund_couple(i) = .False.
normalization_factor_neutra_no_hund_couple(2) += psi_ref_coef_diagonalized(ionic_index(ionicity_level,i),1) **2
endif
enddo
ratio_hund_no_hund = coef_ref_no_hund/coef_ref_hund
normalization_factor_neutra_no_hund_couple(1) = 1.d0/dsqrt(normalization_factor_neutra_no_hund_couple(1))
normalization_factor_neutra_no_hund_couple(2) = 1.d0/dsqrt(normalization_factor_neutra_no_hund_couple(2))
print*,'number_neutral_no_hund_couples = ',number_neutral_no_hund_couples
END_PROVIDER
BEGIN_PROVIDER [double precision, H_OVB_naked_first_ionic, (2,min_number_ionic:max_number_ionic,n_states)]
&BEGIN_PROVIDER [double precision, H_OVB_naked_first_ionic_between_ionic, (2,2,n_states)]
BEGIN_DOC
! H_OVB_naked_first_ionic(1,i) = H_matrix element between the first ionic determinants belonging to is_a_first_ionic_couple = True
! and the contracted ith ionic form
! if i == 1 not defined
! H_OVB_naked_first_ionic(2,i) = H_matrix element between the first ionic determinants belonging to is_a_first_ionic_couple = False
! and the contracted ith ionic form
! if i == 1 not defined
! H_OVB_naked_first_ionic_between_ionic(1,1) = H_matrix element between the first ionic determinants belonging to is_a_first_ionic_couple = True
! and the first ionic determinants belonging to is_a_first_ionic_couple = True
! H_OVB_naked_first_ionic_between_ionic(1,2) = H_matrix element between the first ionic determinants belonging to is_a_first_ionic_couple = True
! and the first ionic determinants belonging to is_a_first_ionic_couple = False
! H_OVB_naked_first_ionic_between_ionic(2,2) = H_matrix element between the first ionic determinants belonging to is_a_first_ionic_couple = False
! and the first ionic determinants belonging to is_a_first_ionic_couple = False
END_DOC
implicit none
integer :: i,j,istate,k,l
double precision :: accu_1,accu_2,hij
H_OVB_naked_first_ionic = 0.d0
H_OVB_naked_first_ionic_between_ionic = 0.d0
i = 1
do j = min_number_ionic,max_number_ionic
if(j==1)cycle
do istate = 1, N_states
accu_1 = 0.d0
accu_2 = 0.d0
do k = 1, ionic_index(i,0)
if(is_a_first_ionic_couple(k))then
do l = 1, ionic_index(j,0)
hij = ref_hamiltonian_matrix(ionic_index(i,k),ionic_index(j,l))
accu_1 += psi_ref_coef_diagonalized(ionic_index(i,k),istate) * normalization_factor_special_first_ionic(1) * &
psi_ref_coef_diagonalized(ionic_index(j,l),istate) * normalization_factor_ionic(j,istate) * hij
enddo
else
do l = 1, ionic_index(j,0)
hij = ref_hamiltonian_matrix(ionic_index(i,k),ionic_index(j,l))
accu_2 += psi_ref_coef_diagonalized(ionic_index(i,k),istate) * normalization_factor_special_first_ionic(2) * &
psi_ref_coef_diagonalized(ionic_index(j,l),istate) * normalization_factor_ionic(j,istate) * hij
enddo
endif
enddo
H_OVB_naked_first_ionic(1,j,istate) = accu_1
H_OVB_naked_first_ionic(2,j,istate) = accu_2
enddo
enddo
do istate = 1, N_states
accu_1 = 0.d0
accu_2 = 0.d0
integer :: i_count
i_count = 0
do k = 1, ionic_index(1,0)
do l = 1, ionic_index(1,0)
hij = ref_hamiltonian_matrix(ionic_index(1,k),ionic_index(1,l))
accu_1 = hij * psi_ref_coef_diagonalized(ionic_index(1,k),istate) * psi_ref_coef_diagonalized(ionic_index(1,l),istate)
if(is_a_first_ionic_couple(k).and. is_a_first_ionic_couple(l))then
H_OVB_naked_first_ionic_between_ionic(1,1,istate) += accu_1 * normalization_factor_special_first_ionic(1) **2
elseif(is_a_first_ionic_couple(k).and. .not.is_a_first_ionic_couple(l))then
i_count += 1
H_OVB_naked_first_ionic_between_ionic(1,2,istate) += accu_1 * &
normalization_factor_special_first_ionic(1) *normalization_factor_special_first_ionic(2)
! elseif(is_a_first_ionic_couple(l).and. .not.is_a_first_ionic_couple(k))then
! i_count += 1
! H_OVB_naked_first_ionic_between_ionic(1,2,istate) += accu_1 * &
! normalization_factor_special_first_ionic(1) *normalization_factor_special_first_ionic(2)
elseif(.not.is_a_first_ionic_couple(k).and. .not.is_a_first_ionic_couple(l))then
H_OVB_naked_first_ionic_between_ionic(2,2,istate) += accu_1 * normalization_factor_special_first_ionic(2) **2
endif
enddo
enddo
enddo
print*,'i_count = ',i_count
print*,'number_first_ionic_couples**2 = ',ionic_index(1,0) * number_first_ionic_couples
double precision :: convert_hartree_ev
convert_hartree_ev = 27.211399d0
print*,'Special H matrix'
do i = 1,2
write(*,'(I4,X,10(F16.8 ,4X))')i, H_OVB_naked_first_ionic(i,:,1)
enddo
print*,'Special H matrix bis'
do i = 1,2
write(*,'(I4,X,10(F16.8 ,4X))')i, H_OVB_naked_first_ionic_between_ionic(i,:,1)
enddo
END_PROVIDER