qp2/src/scf_utils/roothaan_hall_scf.irp.f

subroutine Roothaan_Hall_SCF

BEGIN_DOC
! Roothaan-Hall algorithm for SCF Hartree-Fock calculation
END_DOC

  implicit none

  double precision               :: energy_SCF,energy_SCF_previous,Delta_energy_SCF
  double precision               :: max_error_DIIS,max_error_DIIS_alpha,max_error_DIIS_beta
  double precision, allocatable  :: Fock_matrix_DIIS(:,:,:),error_matrix_DIIS(:,:,:)

  integer                        :: iteration_SCF,dim_DIIS,index_dim_DIIS

  logical                        :: converged
  integer                        :: i,j,m
  logical, external              :: qp_stop
  double precision, allocatable :: mo_coef_save(:,:), S(:,:)

  PROVIDE ao_md5 mo_occ level_shift

  allocate(mo_coef_save(ao_num,mo_num),                          &
      Fock_matrix_DIIS (ao_num,ao_num,max_dim_DIIS),                 &
      error_matrix_DIIS(ao_num,ao_num,max_dim_DIIS)                  &
      )

  Fock_matrix_DIIS = 0.d0
  error_matrix_DIIS = 0.d0
  mo_coef_save = 0.d0

  call write_time(6)

  print*,'Energy of the guess = ',SCF_energy
  write(6,'(A4, 1X, A16, 1X, A16, 1X, A16, 1X, A16)')  &
    '====','================','================','================','================'
  write(6,'(A4, 1X, A16, 1X, A16, 1X, A16, 1X, A16)')  &
    '  N ', 'Energy  ', 'Energy diff  ',  'DIIS error  ', 'Level shift   '
  write(6,'(A4, 1X, A16, 1X, A16, 1X, A16, 1X, A16)')  &
    '====','================','================','================','================'

! Initialize energies and density matrices
  energy_SCF_previous = SCF_energy
  Delta_energy_SCF    = 1.d0
  iteration_SCF       = 0
  dim_DIIS            = 0
  max_error_DIIS      = 1.d0


!
! Start of main SCF loop
!
  PROVIDE FPS_SPF_matrix_AO Fock_matrix_AO 

  converged = .False.
  do while ( .not.converged .and. (iteration_SCF < n_it_SCF_max) )

! Increment cycle number

    iteration_SCF += 1
    if(frozen_orb_scf)then
     call initialize_mo_coef_begin_iteration
    endif

! Current size of the DIIS space

    dim_DIIS = min(dim_DIIS+1,max_dim_DIIS)

    if ( (scf_algorithm == 'DIIS').and.(dabs(Delta_energy_SCF) > 1.d-6) )  then

      ! Store Fock and error matrices at each iteration
      do j=1,ao_num
        do i=1,ao_num
          index_dim_DIIS = mod(dim_DIIS-1,max_dim_DIIS)+1
          Fock_matrix_DIIS (i,j,index_dim_DIIS) = Fock_matrix_AO(i,j)
          error_matrix_DIIS(i,j,index_dim_DIIS) = FPS_SPF_matrix_AO(i,j)
        enddo
      enddo

      ! Compute the extrapolated Fock matrix

      call extrapolate_Fock_matrix(                                    &
          error_matrix_DIIS,Fock_matrix_DIIS,                          &
          Fock_matrix_AO,size(Fock_matrix_AO,1),                       &
          iteration_SCF,dim_DIIS                                       &
          )

      Fock_matrix_AO_alpha = Fock_matrix_AO*0.5d0
      Fock_matrix_AO_beta  = Fock_matrix_AO*0.5d0
      TOUCH Fock_matrix_AO_alpha Fock_matrix_AO_beta

    endif

    MO_coef = eigenvectors_Fock_matrix_MO
    if(frozen_orb_scf)then
     call reorder_core_orb
     call initialize_mo_coef_begin_iteration
    endif

    TOUCH MO_coef

!   Calculate error vectors

    max_error_DIIS = maxval(Abs(FPS_SPF_Matrix_MO))

!   SCF energy

    energy_SCF = SCF_energy
    Delta_Energy_SCF = energy_SCF - energy_SCF_previous
    if ( (SCF_algorithm == 'DIIS').and.(Delta_Energy_SCF > 0.d0) ) then
      Fock_matrix_AO(1:ao_num,1:ao_num) = Fock_matrix_DIIS (1:ao_num,1:ao_num,index_dim_DIIS)
      Fock_matrix_AO_alpha = Fock_matrix_AO*0.5d0
      Fock_matrix_AO_beta  = Fock_matrix_AO*0.5d0
      TOUCH Fock_matrix_AO_alpha Fock_matrix_AO_beta
    endif

    double precision :: level_shift_save
    level_shift_save = level_shift
    mo_coef_save(1:ao_num,1:mo_num) = mo_coef(1:ao_num,1:mo_num)
    do while (Delta_energy_SCF > 0.d0)
      mo_coef(1:ao_num,1:mo_num) = mo_coef_save
      if (level_shift <= .1d0) then
        level_shift = 1.d0
      else
        level_shift = level_shift * 3.0d0
      endif
      TOUCH mo_coef level_shift
      mo_coef(1:ao_num,1:mo_num) = eigenvectors_Fock_matrix_MO(1:ao_num,1:mo_num)
      if(frozen_orb_scf)then
        call reorder_core_orb
        call initialize_mo_coef_begin_iteration
      endif
      TOUCH mo_coef
      Delta_Energy_SCF = SCF_energy - energy_SCF_previous
      energy_SCF = SCF_energy
      if (level_shift-level_shift_save > 40.d0) then
        level_shift = level_shift_save * 4.d0
        SOFT_TOUCH level_shift
        exit
      endif
      dim_DIIS=0
    enddo
    level_shift = level_shift * 0.5d0
    SOFT_TOUCH level_shift
    energy_SCF_previous = energy_SCF

    converged = ( (max_error_DIIS <= threshold_DIIS_nonzero) .and. &
                  (dabs(Delta_energy_SCF) <= thresh_SCF) )

!   Print results at the end of each iteration

    write(6,'(I4, 1X, F16.10, 1X, F16.10, 1X, F16.10, 1X, F16.10, 1X, I3)')  &
      iteration_SCF, energy_SCF, Delta_energy_SCF, max_error_DIIS, level_shift, dim_DIIS

!   Write data in JSON file

    call lock_io
    if (iteration_SCF == 1) then
      write(json_unit, json_dict_uopen_fmt)
    else
      write(json_unit, json_dict_close_uopen_fmt)
    endif
    write(json_unit, json_int_fmt) 'iteration', iteration_SCF
    write(json_unit, json_real_fmt) 'energy', energy_SCF
    write(json_unit, json_real_fmt) 'delta_energy_SCF', Delta_energy_SCF
    write(json_unit, json_real_fmt) 'max_error_DIIS', max_error_DIIS
    write(json_unit, json_real_fmt) 'level_shift', level_shift
    write(json_unit, json_int_fmt) 'dim_DIIS', dim_DIIS
    call unlock_io

    if (Delta_energy_SCF < 0.d0) then
      call save_mos
      write(json_unit, json_true_fmt) 'saved'
    else
      write(json_unit, json_false_fmt) 'saved'
    endif

    call lock_io
    if (converged) then
      write(json_unit, json_true_fmtx) 'converged'
    else
      write(json_unit, json_false_fmtx) 'converged'
    endif
    call unlock_io

    if (qp_stop()) exit

  enddo
  write(json_unit, json_dict_close_fmtx)

 if (iteration_SCF < n_it_SCF_max) then
   mo_label = 'Canonical'
 endif
!
! End of Main SCF loop
!

  write(6,'(A4, 1X, A16, 1X, A16, 1X, A16, 1X, A16)')  &
    '====','================','================','================','================'
  write(6,*)
  if (converged) then
    write(6,*) 'SCF converged'
    call sleep(1)   ! When too fast, the MOs aren't saved.
  endif


  if(.not.frozen_orb_scf)then
   call mo_as_eigvectors_of_mo_matrix(Fock_matrix_mo,size(Fock_matrix_mo,1), &
      size(Fock_matrix_mo,2),mo_label,1,.true.)
   call restore_symmetry(ao_num, mo_num, mo_coef, size(mo_coef,1), 1.d-10)
   call orthonormalize_mos
  endif


  ! Identify degenerate MOs and force them on the axes
  allocate(S(ao_num,ao_num))
  i=1
  do while (i<mo_num)
    j=i
    m=1
    do while ( (j<mo_num).and.(fock_matrix_diag_mo(j+1)-fock_matrix_diag_mo(i) < 1.d-8) )
      j += 1
      m += 1
    enddo
    if (m>1) then
      call dgemm('N','T',ao_num,ao_num,m,1.d0,mo_coef(1,i),size(mo_coef,1),mo_coef(1,i),size(mo_coef,1),0.d0,S,size(S,1))
      call pivoted_cholesky( S, m, -1.d0, ao_num, mo_coef(1,i))
    endif
    i = j+1
  enddo


  call save_mos

  call write_double(6, Energy_SCF, 'SCF energy')

  call write_time(6)

end

subroutine extrapolate_Fock_matrix(               &
           error_matrix_DIIS,Fock_matrix_DIIS,    &
           Fock_matrix_AO_,size_Fock_matrix_AO,   &
           iteration_SCF,dim_DIIS                 &
           )

BEGIN_DOC
! Compute the extrapolated Fock matrix using the DIIS procedure
END_DOC

  implicit none

  integer,intent(inout)         :: dim_DIIS
  double precision,intent(in)   :: Fock_matrix_DIIS(ao_num,ao_num,dim_DIIS),error_matrix_DIIS(ao_num,ao_num,dim_DIIS)
  integer,intent(in)            :: iteration_SCF, size_Fock_matrix_AO
  double precision,intent(inout):: Fock_matrix_AO_(size_Fock_matrix_AO,ao_num)

  double precision,allocatable  :: B_matrix_DIIS(:,:),X_vector_DIIS(:)
  double precision,allocatable  :: C_vector_DIIS(:)

  double precision,allocatable  :: scratch(:,:)
  integer                       :: i,j,k,l,i_DIIS,j_DIIS
  double precision :: rcond, ferr, berr
  integer, allocatable :: iwork(:)
  integer :: lwork

  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_SCF-j,max_dim_DIIS)+1)

    do i=1,dim_DIIS
      i_DIIS = min(dim_DIIS,mod(iteration_SCF-i,max_dim_DIIS)+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) + &
            error_matrix_DIIS(k,l,i_DIIS) * error_matrix_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
  double precision :: anorm
  integer              :: info
  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_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 DIIS'
  endif

  ! Compute extrapolated Fock matrix


  !$OMP PARALLEL DO PRIVATE(i,j,k) DEFAULT(SHARED) if (ao_num > 200)
  do j=1,ao_num
    do i=1,ao_num
      Fock_matrix_AO_(i,j) = 0.d0
    enddo
    do k=1,dim_DIIS
      if (dabs(X_vector_DIIS(k)) < 1.d-10) cycle
      do i=1,ao_num
        ! FPE here
        Fock_matrix_AO_(i,j) = Fock_matrix_AO_(i,j) +            &
            X_vector_DIIS(k)*Fock_matrix_DIIS(i,j,dim_DIIS-k+1)
      enddo
    enddo
  enddo
  !$OMP END PARALLEL DO

end