mirror of
https://github.com/QuantumPackage/qp2.git
synced 2024-06-01 18:25:17 +02:00
337 lines
10 KiB
Fortran
337 lines
10 KiB
Fortran
! ---
|
|
|
|
subroutine rh_tcscf()
|
|
|
|
BEGIN_DOC
|
|
!
|
|
! Roothaan-Hall algorithm for TC-SCF calculation
|
|
!
|
|
END_DOC
|
|
|
|
implicit none
|
|
|
|
integer :: i, j
|
|
integer :: iteration_TCSCF, dim_DIIS, index_dim_DIIS
|
|
double precision :: energy_TCSCF, energy_TCSCF_1e, energy_TCSCF_2e, energy_TCSCF_3e, gradie_TCSCF
|
|
double precision :: energy_TCSCF_previous, delta_energy_TCSCF
|
|
double precision :: gradie_TCSCF_previous, delta_gradie_TCSCF
|
|
double precision :: max_error_DIIS_TCSCF
|
|
double precision :: level_shift_save
|
|
double precision :: delta_energy_tmp, delta_gradie_tmp
|
|
double precision, allocatable :: F_DIIS(:,:,:), e_DIIS(:,:,:)
|
|
double precision, allocatable :: mo_r_coef_save(:,:), mo_l_coef_save(:,:)
|
|
|
|
logical, external :: qp_stop
|
|
|
|
|
|
!PROVIDE ao_md5 mo_occ
|
|
PROVIDE level_shift_TCSCF
|
|
|
|
allocate( mo_r_coef_save(ao_num,mo_num), mo_l_coef_save(ao_num,mo_num) &
|
|
, F_DIIS(ao_num,ao_num,max_dim_DIIS_TCSCF), e_DIIS(ao_num,ao_num,max_dim_DIIS_TCSCF) )
|
|
|
|
F_DIIS = 0.d0
|
|
e_DIIS = 0.d0
|
|
mo_l_coef_save = 0.d0
|
|
mo_r_coef_save = 0.d0
|
|
|
|
call write_time(6)
|
|
|
|
! ---
|
|
! Initialize energies and density matrices
|
|
|
|
energy_TCSCF_previous = TC_HF_energy
|
|
energy_TCSCF_1e = TC_HF_one_e_energy
|
|
energy_TCSCF_2e = TC_HF_two_e_energy
|
|
energy_TCSCF_3e = 0.d0
|
|
if(three_body_h_tc) then
|
|
energy_TCSCF_3e = diag_three_elem_hf
|
|
endif
|
|
gradie_TCSCF_previous = grad_non_hermit
|
|
delta_energy_TCSCF = 1.d0
|
|
delta_gradie_TCSCF = 1.d0
|
|
iteration_TCSCF = 0
|
|
dim_DIIS = 0
|
|
max_error_DIIS_TCSCF = 1.d0
|
|
|
|
! ---
|
|
|
|
! Start of main SCF loop
|
|
|
|
PROVIDE FQS_SQF_ao Fock_matrix_tc_ao_tot
|
|
|
|
do while( (max_error_DIIS_TCSCF > threshold_DIIS_nonzero_TCSCF) .or. &
|
|
!(dabs(delta_energy_TCSCF) > thresh_TCSCF) .or. &
|
|
(dabs(gradie_TCSCF_previous) > dsqrt(thresh_TCSCF)) )
|
|
|
|
iteration_TCSCF += 1
|
|
if(iteration_TCSCF > n_it_TCSCF_max) then
|
|
print *, ' max of TCSCF iterations is reached ', n_it_TCSCF_max
|
|
stop
|
|
endif
|
|
|
|
dim_DIIS = min(dim_DIIS+1, max_dim_DIIS_TCSCF)
|
|
|
|
! ---
|
|
|
|
if((tcscf_algorithm == 'DIIS') .and. (dabs(delta_energy_TCSCF) > 1.d-6)) then
|
|
|
|
! store Fock and error matrices at each iteration
|
|
index_dim_DIIS = mod(dim_DIIS-1, max_dim_DIIS_TCSCF) + 1
|
|
do j = 1, ao_num
|
|
do i = 1, ao_num
|
|
F_DIIS(i,j,index_dim_DIIS) = Fock_matrix_tc_ao_tot(i,j)
|
|
e_DIIS(i,j,index_dim_DIIS) = FQS_SQF_ao(i,j)
|
|
enddo
|
|
enddo
|
|
|
|
call extrapolate_TC_Fock_matrix(e_DIIS, F_DIIS, Fock_matrix_tc_ao_tot, size(Fock_matrix_tc_ao_tot, 1), iteration_TCSCF, dim_DIIS)
|
|
|
|
Fock_matrix_tc_ao_alpha = 0.5d0 * Fock_matrix_tc_ao_tot
|
|
Fock_matrix_tc_ao_beta = 0.5d0 * Fock_matrix_tc_ao_tot
|
|
!TOUCH Fock_matrix_tc_ao_alpha Fock_matrix_tc_ao_beta
|
|
|
|
call ao_to_mo_bi_ortho( Fock_matrix_tc_ao_alpha, size(Fock_matrix_tc_ao_alpha, 1) &
|
|
, Fock_matrix_tc_mo_alpha, size(Fock_matrix_tc_mo_alpha, 1) )
|
|
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) )
|
|
TOUCH Fock_matrix_tc_mo_alpha Fock_matrix_tc_mo_beta
|
|
endif
|
|
|
|
! ---
|
|
|
|
mo_l_coef(1:ao_num,1:mo_num) = fock_tc_leigvec_ao(1:ao_num,1:mo_num)
|
|
mo_r_coef(1:ao_num,1:mo_num) = fock_tc_reigvec_ao(1:ao_num,1:mo_num)
|
|
TOUCH mo_l_coef mo_r_coef
|
|
|
|
! ---
|
|
|
|
! calculate error vectors
|
|
max_error_DIIS_TCSCF = maxval(abs(FQS_SQF_mo))
|
|
|
|
! ---
|
|
|
|
delta_energy_tmp = TC_HF_energy - energy_TCSCF_previous
|
|
delta_gradie_tmp = grad_non_hermit - gradie_TCSCF_previous
|
|
|
|
! ---
|
|
|
|
do while((delta_gradie_tmp > 1.d-7) .and. (iteration_TCSCF > 1))
|
|
!do while((dabs(delta_energy_tmp) > 0.5d0) .and. (iteration_TCSCF > 1))
|
|
print *, ' very big or bad step : ', delta_energy_tmp, delta_gradie_tmp
|
|
print *, ' TC level shift = ', level_shift_TCSCF
|
|
|
|
mo_l_coef(1:ao_num,1:mo_num) = mo_l_coef_save(1:ao_num,1:mo_num)
|
|
mo_r_coef(1:ao_num,1:mo_num) = mo_r_coef_save(1:ao_num,1:mo_num)
|
|
|
|
if(level_shift_TCSCF <= .1d0) then
|
|
level_shift_TCSCF = 1.d0
|
|
else
|
|
level_shift_TCSCF = level_shift_TCSCF * 3.0d0
|
|
endif
|
|
TOUCH mo_l_coef mo_r_coef level_shift_TCSCF
|
|
|
|
mo_l_coef(1:ao_num,1:mo_num) = fock_tc_leigvec_ao(1:ao_num,1:mo_num)
|
|
mo_r_coef(1:ao_num,1:mo_num) = fock_tc_reigvec_ao(1:ao_num,1:mo_num)
|
|
TOUCH mo_l_coef mo_r_coef
|
|
|
|
delta_energy_tmp = TC_HF_energy - energy_TCSCF_previous
|
|
delta_gradie_tmp = grad_non_hermit - gradie_TCSCF_previous
|
|
|
|
if(level_shift_TCSCF - level_shift_save > 40.d0) then
|
|
level_shift_TCSCF = level_shift_save * 4.d0
|
|
SOFT_TOUCH level_shift_TCSCF
|
|
exit
|
|
endif
|
|
|
|
dim_DIIS = 0
|
|
enddo
|
|
! print *, ' very big step : ', delta_energy_tmp
|
|
! print *, ' TC level shift = ', level_shift_TCSCF
|
|
|
|
! ---
|
|
|
|
level_shift_TCSCF = 0.d0
|
|
!level_shift_TCSCF = level_shift_TCSCF * 0.5d0
|
|
SOFT_TOUCH level_shift_TCSCF
|
|
|
|
gradie_TCSCF = grad_non_hermit
|
|
energy_TCSCF = TC_HF_energy
|
|
energy_TCSCF_1e = TC_HF_one_e_energy
|
|
energy_TCSCF_2e = TC_HF_two_e_energy
|
|
energy_TCSCF_3e = 0.d0
|
|
if(three_body_h_tc) then
|
|
energy_TCSCF_3e = diag_three_elem_hf
|
|
endif
|
|
delta_energy_TCSCF = energy_TCSCF - energy_TCSCF_previous
|
|
delta_gradie_TCSCF = gradie_TCSCF - gradie_TCSCF_previous
|
|
|
|
energy_TCSCF_previous = energy_TCSCF
|
|
gradie_TCSCF_previous = gradie_TCSCF
|
|
|
|
|
|
level_shift_save = level_shift_TCSCF
|
|
mo_l_coef_save(1:ao_num,1:mo_num) = mo_l_coef(1:ao_num,1:mo_num)
|
|
mo_r_coef_save(1:ao_num,1:mo_num) = mo_r_coef(1:ao_num,1:mo_num)
|
|
|
|
|
|
print *, ' iteration = ', iteration_TCSCF
|
|
print *, ' total TC energy = ', energy_TCSCF
|
|
print *, ' 1-e TC energy = ', energy_TCSCF_1e
|
|
print *, ' 2-e TC energy = ', energy_TCSCF_2e
|
|
print *, ' 3-e TC energy = ', energy_TCSCF_3e
|
|
print *, ' |delta TC energy| = ', dabs(delta_energy_TCSCF)
|
|
print *, ' TC gradient = ', gradie_TCSCF
|
|
print *, ' delta TC gradient = ', delta_gradie_TCSCF
|
|
print *, ' max TC DIIS error = ', max_error_DIIS_TCSCF
|
|
print *, ' TC DIIS dim = ', dim_DIIS
|
|
print *, ' TC level shift = ', level_shift_TCSCF
|
|
print *, ' '
|
|
|
|
call ezfio_set_bi_ortho_mos_mo_l_coef(mo_l_coef)
|
|
call ezfio_set_bi_ortho_mos_mo_r_coef(mo_r_coef)
|
|
|
|
if(qp_stop()) exit
|
|
enddo
|
|
|
|
! ---
|
|
|
|
print *, ' TCSCF DIIS converged !'
|
|
call print_energy_and_mos()
|
|
|
|
call write_time(6)
|
|
|
|
deallocate(mo_r_coef_save, mo_l_coef_save, F_DIIS, e_DIIS)
|
|
|
|
end
|
|
|
|
! ---
|
|
|
|
subroutine extrapolate_TC_Fock_matrix(e_DIIS, F_DIIS, F_ao, size_F_ao, iteration_TCSCF, dim_DIIS)
|
|
|
|
BEGIN_DOC
|
|
!
|
|
! Compute the extrapolated Fock matrix using the DIIS procedure
|
|
!
|
|
! e = \sum_i c_i e_i and \sum_i c_i = 1
|
|
! ==> lagrange multiplier with L = |e|^2 - \lambda (\sum_i c_i = 1)
|
|
!
|
|
END_DOC
|
|
|
|
implicit none
|
|
|
|
integer, intent(in) :: iteration_TCSCF, size_F_ao
|
|
integer, intent(inout) :: dim_DIIS
|
|
double precision, intent(in) :: F_DIIS(ao_num,ao_num,dim_DIIS)
|
|
double precision, intent(in) :: e_DIIS(ao_num,ao_num,dim_DIIS)
|
|
double precision, intent(inout) :: F_ao(size_F_ao,ao_num)
|
|
|
|
double precision, allocatable :: B_matrix_DIIS(:,:), X_vector_DIIS(:), C_vector_DIIS(:)
|
|
|
|
integer :: i, j, k, l, i_DIIS, j_DIIS
|
|
integer :: lwork
|
|
double precision :: rcond, ferr, berr
|
|
integer, allocatable :: iwork(:)
|
|
double precision, allocatable :: scratch(:,:)
|
|
|
|
if(dim_DIIS < 1) then
|
|
return
|
|
endif
|
|
|
|
allocate( B_matrix_DIIS(dim_DIIS+1,dim_DIIS+1), X_vector_DIIS(dim_DIIS+1) &
|
|
, C_vector_DIIS(dim_DIIS+1), scratch(ao_num,ao_num) )
|
|
|
|
! Compute the matrices B and X
|
|
B_matrix_DIIS(:,:) = 0.d0
|
|
do j = 1, dim_DIIS
|
|
j_DIIS = min(dim_DIIS, mod(iteration_TCSCF-j, max_dim_DIIS_TCSCF)+1)
|
|
|
|
do i = 1, dim_DIIS
|
|
i_DIIS = min(dim_DIIS, mod(iteration_TCSCF-i, max_dim_DIIS_TCSCF)+1)
|
|
|
|
! Compute product of two errors vectors
|
|
do l = 1, ao_num
|
|
do k = 1, ao_num
|
|
B_matrix_DIIS(i,j) = B_matrix_DIIS(i,j) + e_DIIS(k,l,i_DIIS) * e_DIIS(k,l,j_DIIS)
|
|
enddo
|
|
enddo
|
|
|
|
enddo
|
|
enddo
|
|
|
|
! Pad B matrix and build the X matrix
|
|
|
|
C_vector_DIIS(:) = 0.d0
|
|
do i = 1, dim_DIIS
|
|
B_matrix_DIIS(i,dim_DIIS+1) = -1.d0
|
|
B_matrix_DIIS(dim_DIIS+1,i) = -1.d0
|
|
enddo
|
|
C_vector_DIIS(dim_DIIS+1) = -1.d0
|
|
|
|
deallocate(scratch)
|
|
|
|
! Estimate condition number of B
|
|
integer :: info
|
|
double precision :: anorm
|
|
integer, allocatable :: ipiv(:)
|
|
double precision, allocatable :: AF(:,:)
|
|
double precision, external :: dlange
|
|
|
|
lwork = max((dim_DIIS+1)**2, (dim_DIIS+1)*5)
|
|
allocate(AF(dim_DIIS+1,dim_DIIS+1))
|
|
allocate(ipiv(2*(dim_DIIS+1)), iwork(2*(dim_DIIS+1)) )
|
|
allocate(scratch(lwork,1))
|
|
scratch(:,1) = 0.d0
|
|
|
|
anorm = dlange('1', dim_DIIS+1, dim_DIIS+1, B_matrix_DIIS, size(B_matrix_DIIS, 1), scratch(1,1))
|
|
|
|
AF(:,:) = B_matrix_DIIS(:,:)
|
|
call dgetrf(dim_DIIS+1, dim_DIIS+1, AF, size(AF, 1), ipiv, info)
|
|
if(info /= 0) then
|
|
dim_DIIS = 0
|
|
return
|
|
endif
|
|
|
|
call dgecon('1', dim_DIIS+1, AF, size(AF, 1), anorm, rcond, scratch, iwork, info)
|
|
if(info /= 0) then
|
|
dim_DIIS = 0
|
|
return
|
|
endif
|
|
|
|
if(rcond < 1.d-14) then
|
|
dim_DIIS = 0
|
|
return
|
|
endif
|
|
|
|
! solve the linear system C = B x X
|
|
|
|
X_vector_DIIS = C_vector_DIIS
|
|
call dgesv(dim_DIIS+1, 1, B_matrix_DIIS, size(B_matrix_DIIS, 1), ipiv , X_vector_DIIS, size(X_vector_DIIS, 1), info)
|
|
|
|
deallocate(scratch, AF, iwork)
|
|
if(info < 0) then
|
|
stop ' bug in TC-DIIS'
|
|
endif
|
|
|
|
! Compute extrapolated Fock matrix
|
|
|
|
!$OMP PARALLEL DO PRIVATE(i,j,k) DEFAULT(SHARED) if (ao_num > 200)
|
|
do j = 1, ao_num
|
|
do i = 1, ao_num
|
|
F_ao(i,j) = 0.d0
|
|
enddo
|
|
do k = 1, dim_DIIS
|
|
if(dabs(X_vector_DIIS(k)) < 1.d-10) cycle
|
|
do i = 1,ao_num
|
|
! FPE here
|
|
F_ao(i,j) = F_ao(i,j) + X_vector_DIIS(k) * F_DIIS(i,j,dim_DIIS-k+1)
|
|
enddo
|
|
enddo
|
|
enddo
|
|
!$OMP END PARALLEL DO
|
|
|
|
end
|
|
|
|
! ---
|
|
|