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