mirror of https://github.com/pfloos/quack
453 lines
15 KiB
Fortran
453 lines
15 KiB
Fortran
subroutine qsGGW(dotest,maxSCF,thresh,max_diis,doACFDT,exchange_kernel,doXBS,dophBSE,dophBSE2,TDA_W,TDA,dBSE,dTDA,doppBSE, &
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eta,regularize,nNuc,ZNuc,rNuc,ENuc,nBas,nBas2,nC,nO,nV,nR,nS,EGHF,Ov,Or,T,V,Hc,ERI_AO, &
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ERI_MO,dipole_int_AO,dipole_int_MO,PHF,cHF,eHF)
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! Generalized version of quasiparticle self-consistent GW
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implicit none
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include 'parameters.h'
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! Input variables
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logical,intent(in) :: dotest
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integer,intent(in) :: maxSCF
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integer,intent(in) :: max_diis
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double precision,intent(in) :: thresh
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logical,intent(in) :: doACFDT
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logical,intent(in) :: exchange_kernel
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logical,intent(in) :: doXBS
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logical,intent(in) :: dophBSE
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logical,intent(in) :: dophBSE2
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logical,intent(in) :: TDA_W
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logical,intent(in) :: TDA
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logical,intent(in) :: dBSE
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logical,intent(in) :: dTDA
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logical,intent(in) :: doppBSE
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double precision,intent(in) :: eta
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logical,intent(in) :: regularize
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integer,intent(in) :: nNuc
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double precision,intent(in) :: ZNuc(nNuc)
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double precision,intent(in) :: rNuc(nNuc,ncart)
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double precision,intent(in) :: ENuc
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integer,intent(in) :: nBas
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integer,intent(in) :: nBas2
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integer,intent(in) :: nC
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integer,intent(in) :: nO
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integer,intent(in) :: nV
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integer,intent(in) :: nR
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integer,intent(in) :: nS
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double precision,intent(in) :: EGHF
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double precision,intent(in) :: eHF(nBas2)
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double precision,intent(in) :: cHF(nBas2,nBas2)
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double precision,intent(in) :: PHF(nBas2,nBas2)
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double precision,intent(in) :: Ov(nBas,nBas)
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double precision,intent(in) :: T(nBas,nBas)
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double precision,intent(in) :: V(nBas,nBas)
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double precision,intent(in) :: Hc(nBas,nBas)
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double precision,intent(in) :: Or(nBas,nBas)
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double precision,intent(in) :: ERI_AO(nBas,nBas,nBas,nBas)
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double precision,intent(inout):: ERI_MO(nBas2,nBas2,nBas2,nBas2)
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double precision,intent(in) :: dipole_int_AO(nBas,nBas,ncart)
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double precision,intent(inout):: dipole_int_MO(nBas2,nBas2,ncart)
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! Local variables
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integer :: nSCF
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integer :: nBasSq
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integer :: nBas2Sq
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integer :: ispin
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integer :: ixyz
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integer :: n_diis
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double precision :: ET,ETaa,ETbb
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double precision :: EV,EVaa,EVbb
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double precision :: EJ,EJaaaa,EJaabb,EJbbaa,EJbbbb
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double precision :: EK,EKaaaa,EKabba,EKbaab,EKbbbb
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double precision :: EqsGW
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double precision :: EcRPA
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double precision :: EcBSE
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double precision :: EcGM
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double precision :: Conv
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double precision :: rcond
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double precision,external :: trace_matrix
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double precision :: dipole(ncart)
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logical :: dRPA = .true.
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logical :: print_W = .true.
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double precision,allocatable :: err_diis(:,:)
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double precision,allocatable :: F_diis(:,:)
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double precision,allocatable :: Aph(:,:)
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double precision,allocatable :: Bph(:,:)
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double precision,allocatable :: Om(:)
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double precision,allocatable :: XpY(:,:)
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double precision,allocatable :: XmY(:,:)
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double precision,allocatable :: rho(:,:,:)
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double precision,allocatable :: Ca(:,:),Cb(:,:)
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double precision,allocatable :: ERI_tmp(:,:,:,:)
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double precision,allocatable :: Jaa(:,:),Jbb(:,:)
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double precision,allocatable :: Kaa(:,:),Kab(:,:),Kba(:,:),Kbb(:,:)
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double precision,allocatable :: Faa(:,:),Fab(:,:),Fba(:,:),Fbb(:,:)
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double precision,allocatable :: Paa(:,:),Pab(:,:),Pba(:,:),Pbb(:,:)
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double precision,allocatable :: C(:,:)
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double precision,allocatable :: Cp(:,:)
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double precision,allocatable :: eGW(:)
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double precision,allocatable :: P(:,:)
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double precision,allocatable :: F(:,:)
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double precision,allocatable :: H(:,:)
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double precision,allocatable :: S(:,:)
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double precision,allocatable :: X(:,:)
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double precision,allocatable :: Fp(:,:)
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double precision,allocatable :: SigC(:,:)
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double precision,allocatable :: SigCp(:,:)
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double precision,allocatable :: Z(:)
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double precision,allocatable :: err(:,:)
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! Hello world
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write(*,*)
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write(*,*)'********************************'
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write(*,*)'* Generalized qsGW Calculation *'
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write(*,*)'********************************'
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write(*,*)
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! Warning
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write(*,*) '!! ERIs in MO basis will be overwritten in qsGW !!'
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write(*,*)
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! Stuff
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nBasSq = nBas*nBas
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nBas2Sq = nBas2*nBas2
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! TDA for W
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if(TDA_W) then
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write(*,*) 'Tamm-Dancoff approximation for dynamic screening!'
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write(*,*)
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end if
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! TDA
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if(TDA) then
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write(*,*) 'Tamm-Dancoff approximation activated!'
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write(*,*)
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end if
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! Memory allocation
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allocate(Ca(nBas,nBas2),Cb(nBas,nBas2),P(nBas2,nBas2),Jaa(nBas,nBas),Jbb(nBas,nBas), &
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Kaa(nBas,nBas),Kab(nBas,nBas),Kba(nBas,nBas),Kbb(nBas,nBas), &
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Faa(nBas,nBas),Fab(nBas,nBas),Fba(nBas,nBas),Fbb(nBas,nBas), &
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Paa(nBas,nBas),Pab(nBas,nBas),Pba(nBas,nBas),Pbb(nBas,nBas), &
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F(nBas2,nBas2),Fp(nBas2,nBas2),C(nBas2,nBas2),Cp(nBas2,nBas2), &
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H(nBas2,nBas2),S(nBas2,nBas2),X(nBas2,nBas2),err(nBas2,nBas2), &
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err_diis(nBas2Sq,max_diis),F_diis(nBas2Sq,max_diis), &
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eGW(nBas2),SigC(nBas2,nBas2),SigCp(nBas,nBas),Z(nBas2),Aph(nS,nS),Bph(nS,nS), &
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Om(nS),XpY(nS,nS),XmY(nS,nS),rho(nBas2,nBas2,nS))
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! Initialization
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nSCF = -1
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n_diis = 0
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ispin = 3
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Conv = 1d0
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P(:,:) = PHF(:,:)
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eGW(:) = eHF(:)
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c(:,:) = cHF(:,:)
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F_diis(:,:) = 0d0
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err_diis(:,:) = 0d0
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rcond = 0d0
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! Construct super overlap matrix
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S( : , : ) = 0d0
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S( 1:nBas , 1:nBas ) = Ov(1:nBas,1:nBas)
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S(nBas+1:nBas2,nBas+1:nBas2) = Ov(1:nBas,1:nBas)
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! Construct super orthogonalization matrix
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X( : , : ) = 0d0
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X( 1:nBas , 1:nBas ) = Or(1:nBas,1:nBas)
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X(nBas+1:nBas2,nBas+1:nBas2) = Or(1:nBas,1:nBas)
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! Construct super orthogonalization matrix
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H( : , : ) = 0d0
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H( 1:nBas , 1:nBas ) = Hc(1:nBas,1:nBas)
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H(nBas+1:nBas2,nBas+1:nBas2) = Hc(1:nBas,1:nBas)
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! Construct super density matrix
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P(:,:) = matmul(C(:,1:nO),transpose(C(:,1:nO)))
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Paa(:,:) = P( 1:nBas , 1:nBas )
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Pab(:,:) = P( 1:nBas ,nBas+1:nBas2)
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Pba(:,:) = P(nBas+1:nBas2, 1:nBas )
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Pbb(:,:) = P(nBas+1:nBas2,nBas+1:nBas2)
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!------------------------------------------------------------------------
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! Main loop
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!------------------------------------------------------------------------
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do while(Conv > thresh .and. nSCF <= maxSCF)
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! Increment
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nSCF = nSCF + 1
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! Buid Hartree matrix
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call Hartree_matrix_AO_basis(nBas,Paa,ERI_AO,Jaa)
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call Hartree_matrix_AO_basis(nBas,Pbb,ERI_AO,Jbb)
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! Compute exchange part of the self-energy
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call exchange_matrix_AO_basis(nBas,Paa,ERI_AO,Kaa)
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call exchange_matrix_AO_basis(nBas,Pba,ERI_AO,Kab)
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call exchange_matrix_AO_basis(nBas,Pab,ERI_AO,Kba)
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call exchange_matrix_AO_basis(nBas,Pbb,ERI_AO,Kbb)
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! Build individual Fock matrices
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Faa(:,:) = Hc(:,:) + Jaa(:,:) + Jbb(:,:) + Kaa(:,:)
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Fab(:,:) = + Kab(:,:)
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Fba(:,:) = + Kba(:,:)
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Fbb(:,:) = Hc(:,:) + Jbb(:,:) + Jaa(:,:) + Kbb(:,:)
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! Build super Fock matrix
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F( 1:nBas , 1:nBas ) = Faa(1:nBas,1:nBas)
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F( 1:nBas ,nBas+1:nBas2) = Fab(1:nBas,1:nBas)
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F(nBas+1:nBas2, 1:nBas ) = Fba(1:nBas,1:nBas)
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F(nBas+1:nBas2,nBas+1:nBas2) = Fbb(1:nBas,1:nBas)
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! AO to MO transformation of two-electron integrals
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allocate(ERI_tmp(nBas2,nBas2,nBas2,nBas2))
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Ca(:,:) = C(1:nBas,1:nBas2)
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Cb(:,:) = C(nBas+1:nBas2,1:nBas2)
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do ixyz=1,ncart
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call AOtoMO_GHF(nBas,nBas2,Ca,Cb,dipole_int_AO(:,:,ixyz),dipole_int_MO(:,:,ixyz))
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end do
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call AOtoMO_ERI_GHF(nBas,nBas2,Ca,Ca,ERI_AO,ERI_tmp)
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ERI_MO(:,:,:,:) = ERI_tmp(:,:,:,:)
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call AOtoMO_ERI_GHF(nBas,nBas2,Ca,Cb,ERI_AO,ERI_tmp)
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ERI_MO(:,:,:,:) = ERI_MO(:,:,:,:) + ERI_tmp(:,:,:,:)
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call AOtoMO_ERI_GHF(nBas,nBas2,Cb,Ca,ERI_AO,ERI_tmp)
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ERI_MO(:,:,:,:) = ERI_MO(:,:,:,:) + ERI_tmp(:,:,:,:)
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call AOtoMO_ERI_GHF(nBas,nBas2,Cb,Cb,ERI_AO,ERI_tmp)
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ERI_MO(:,:,:,:) = ERI_MO(:,:,:,:) + ERI_tmp(:,:,:,:)
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deallocate(ERI_tmp)
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! Compute linear response
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call phLR_A(ispin,dRPA,nBas2,nC,nO,nV,nR,nS,1d0,eGW,ERI_MO,Aph)
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if(.not.TDA_W) call phLR_B(ispin,dRPA,nBas2,nC,nO,nV,nR,nS,1d0,ERI_MO,Bph)
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call phLR(TDA_W,nS,Aph,Bph,EcRPA,Om,XpY,XmY)
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if(print_W) call print_excitation_energies('phRPA@GW@GHF','spinorbital',nS,Om)
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! Compute correlation part of the self-energy
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call GW_excitation_density(nBas2,nC,nO,nR,nS,ERI_MO,XpY,rho)
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if(regularize) call GW_regularization(nBas2,nC,nO,nV,nR,nS,eGW,Om,rho)
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call GGW_self_energy(eta,nBas2,nC,nO,nV,nR,nS,eGW,Om,rho,EcGM,SigC,Z)
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! Make correlation self-energy Hermitian and transform it back to AO basis
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SigC = 0.5d0*(SigC + transpose(SigC))
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call MOtoAO_GHF(nBas2,nBas,S,Ca,Cb,SigC,SigCp)
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! ... and add self-energy
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F(:,:) = F(:,:) + SigCp(:,:)
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! Compute commutator and convergence criteria
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err = matmul(F,matmul(P,S)) - matmul(matmul(S,P),F)
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if(nSCF > 1) Conv = maxval(abs(err))
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! DIIS extrapolation
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if(max_diis > 1) then
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n_diis = min(n_diis+1,max_diis)
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call DIIS_extrapolation(rcond,nBas2Sq,nBas2Sq,n_diis,err_diis,F_diis,err,F)
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end if
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! Transform Fock matrix in orthogonal basis
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Fp(:,:) = matmul(transpose(X),matmul(F,X))
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! Diagonalize Fock matrix to get eigenvectors and eigenvalues
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Cp(:,:) = Fp(:,:)
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call diagonalize_matrix(nBas2,Cp,eGW)
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! Back-transform eigenvectors in non-orthogonal basis
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C(:,:) = matmul(X,Cp)
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call AOtoMO_GHF(nBas,nBas2,Ca,Cb,SigCp,SigC)
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! Form super density matrix
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P(:,:) = matmul(C(:,1:nO),transpose(C(:,1:nO)))
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! Compute individual density matrices
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Paa(:,:) = P( 1:nBas , 1:nBas )
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Pab(:,:) = P( 1:nBas ,nBas+1:nBas2)
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Pba(:,:) = P(nBas+1:nBas2, 1:nBas )
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Pbb(:,:) = P(nBas+1:nBas2,nBas+1:nBas2)
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!------------------------------------------------------------------------
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! Compute total energy
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!------------------------------------------------------------------------
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! Kinetic energy
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ETaa = trace_matrix(nBas,matmul(Paa,T))
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ETbb = trace_matrix(nBas,matmul(Pbb,T))
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ET = ETaa + ETbb
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! Potential energy
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EVaa = trace_matrix(nBas,matmul(Paa,V))
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EVbb = trace_matrix(nBas,matmul(Pbb,V))
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EV = EVaa + EVbb
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! Hartree energy
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EJaaaa = 0.5d0*trace_matrix(nBas,matmul(Paa,Jaa))
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EJaabb = 0.5d0*trace_matrix(nBas,matmul(Paa,Jbb))
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EJbbaa = 0.5d0*trace_matrix(nBas,matmul(Pbb,Jaa))
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EJbbbb = 0.5d0*trace_matrix(nBas,matmul(Pbb,Jbb))
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EJ = EJaaaa + EJaabb + EJbbaa + EJbbbb
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! Exchange energy
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EKaaaa = 0.5d0*trace_matrix(nBas,matmul(Paa,Kaa))
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EKabba = 0.5d0*trace_matrix(nBas,matmul(Pab,Kba))
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EKbaab = 0.5d0*trace_matrix(nBas,matmul(Pba,Kab))
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EKbbbb = 0.5d0*trace_matrix(nBas,matmul(Pbb,Kbb))
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EK = EKaaaa + EKabba + EKbaab + EKbbbb
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! Total energy
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EqsGW = ET + EV + EJ + EK
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! Print results
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call dipole_moment(nBas2,P,nNuc,ZNuc,rNuc,dipole_int_AO,dipole)
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call print_qsGGW(nBas,nBas2,nO,nSCF,Conv,thresh,eHF,eGW,c,Ov,SigC,Z,ENuc,ET,EV,EJ,EK,EcGM,EcRPA,EqsGW,dipole)
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end do
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!------------------------------------------------------------------------
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! End main loop
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!------------------------------------------------------------------------
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! Did it actually converge?
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if(nSCF == maxSCF+1) then
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write(*,*)
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write(*,*)'!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!'
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write(*,*)' Convergence failed '
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write(*,*)'!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!'
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write(*,*)
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stop
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end if
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! Perform BSE calculation
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if(dophBSE) then
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call GGW_phBSE(dophBSE2,TDA_W,TDA,dBSE,dTDA,eta,nBas2,nC,nO,nV,nR,nS,ERI_MO,dipole_int_MO,eGW,eGW,EcBSE)
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write(*,*)
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write(*,*)'-------------------------------------------------------------------------------'
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write(*,'(2X,A50,F20.10,A3)') 'Tr@BSE@qsGW@GHF correlation energy = ',EcBSE,' au'
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write(*,'(2X,A50,F20.10,A4)') 'Tr@BSE@qsGW@GHF total energy = ',ENuc + EqsGW + EcBSE,' au'
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write(*,*)'-------------------------------------------------------------------------------'
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write(*,*)
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! Compute the BSE correlation energy via the adiabatic connection
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! if(doACFDT) then
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! write(*,*) '------------------------------------------------------'
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! write(*,*) 'Adiabatic connection version of BSE correlation energy'
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! write(*,*) '------------------------------------------------------'
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! write(*,*)
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! if(doXBS) then
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! write(*,*) '*** scaled screening version (XBS) ***'
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! write(*,*)
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! end if
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! call GW_phACFDT(exchange_kernel,doXBS,.true.,TDA_W,TDA,dophBSE,singlet,triplet,eta,nBas,nC,nO,nV,nR,nS,ERI_MO,eGW,eGW,EcBSE)
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! write(*,*)
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! write(*,*)'-------------------------------------------------------------------------------'
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! write(*,'(2X,A50,F20.10)') 'AC@BSE@qsGW correlation energy (singlet) =',EcBSE(1)
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! write(*,'(2X,A50,F20.10)') 'AC@BSE@qsGW correlation energy (triplet) =',EcBSE(2)
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! write(*,'(2X,A50,F20.10)') 'AC@BSE@qsGW correlation energy =',EcBSE(1) + EcBSE(2)
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! write(*,'(2X,A50,F20.10)') 'AC@BSE@qsGW total energy =',ENuc + EqsGW + EcBSE(1) + EcBSE(2)
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! write(*,*)'-------------------------------------------------------------------------------'
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! write(*,*)
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! end if
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end if
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! if(doppBSE) then
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!
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! call GW_ppBSE(TDA_W,TDA,dBSE,dTDA,singlet,triplet,eta,nBas,nC,nO,nV,nR,nS,ERI_MO,dipole_int_MO,eHF,eGW,EcBSE)
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!
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! write(*,*)
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! write(*,*)'-------------------------------------------------------------------------------'
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! write(*,'(2X,A50,F20.10)') 'Tr@ppBSE@qsGW correlation energy (singlet) =',EcBSE(1)
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! write(*,'(2X,A50,F20.10)') 'Tr@ppBSE@qsGW correlation energy (triplet) =',3d0*EcBSE(2)
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! write(*,'(2X,A50,F20.10)') 'Tr@ppBSE@qsGW correlation energy =',EcBSE(1) + 3d0*EcBSE(2)
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! write(*,'(2X,A50,F20.10)') 'Tr@ppBSE@qsGW total energy =',ENuc + EGHF + EcBSE(1) + 3d0*EcBSE(2)
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! write(*,*)'-------------------------------------------------------------------------------'
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! write(*,*)
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! end if
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! Testing zone
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if(dotest) then
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call dump_test_value('G','qsGW correlation energy',EcRPA)
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call dump_test_value('G','qsGW HOMO energy',eGW(nO))
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call dump_test_value('G','qsGW LUMO energy',eGW(nO+1))
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end if
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end subroutine
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