subroutine unrestricted_individual_energy(x_rung,x_DFA,c_rung,c_DFA,LDA_centered,nEns,wEns,nCC,aCC,nGrid,weight,nBas,AO,dAO, & T,V,ERI,ENuc,eps,Pw,rhow,drhow,J,Fx,FxHF,Fc,P,rho,drho,Ew,occnum,& Cx_choice,doNcentered) ! Compute unrestricted individual energies as well as excitation energies implicit none include 'parameters.h' ! Input variables integer,intent(in) :: x_rung,c_rung integer,intent(in) :: x_DFA,c_DFA logical,intent(in) :: LDA_centered integer,intent(in) :: nEns double precision,intent(in) :: wEns(nEns) integer,intent(in) :: nCC double precision,intent(in) :: aCC(nCC,nEns-1) integer,intent(in) :: nGrid double precision,intent(in) :: weight(nGrid) integer,intent(in) :: nBas double precision,intent(in) :: AO(nBas,nGrid) double precision,intent(in) :: dAO(ncart,nBas,nGrid) double precision,intent(in) :: T(nBas,nBas) double precision,intent(in) :: V(nBas,nBas) double precision,intent(in) :: ERI(nBas,nBas,nBas,nBas) double precision,intent(in) :: ENuc double precision,intent(in) :: eps(nBas,nspin) double precision,intent(in) :: Pw(nBas,nBas,nspin) double precision,intent(in) :: rhow(nGrid,nspin) double precision,intent(in) :: drhow(ncart,nGrid,nspin) double precision,intent(in) :: P(nBas,nBas,nspin,nEns) double precision,intent(in) :: rho(nGrid,nspin,nEns) double precision,intent(in) :: drho(ncart,nGrid,nspin,nEns) double precision,intent(inout):: J(nBas,nBas,nspin) double precision,intent(inout):: Fx(nBas,nBas,nspin) double precision,intent(inout):: FxHF(nBas,nBas,nspin) double precision,intent(inout):: Fc(nBas,nBas,nspin) double precision,intent(in) :: Ew double precision,intent(in) :: occnum(nBas,nspin,nEns) integer,intent(in) :: Cx_choice logical,intent(in) :: doNcentered ! Local variables double precision :: ET(nspin,nEns) double precision :: EV(nspin,nEns) double precision :: EH(nsp,nEns) double precision :: Ex(nspin,nEns) double precision :: Ec(nsp,nEns) double precision :: LZH(nsp) double precision :: LZx(nspin) double precision :: LZc(nsp) double precision :: Eaux(nspin,nEns) double precision :: ExDD(nspin,nEns) double precision :: EcDD(nsp,nEns) double precision :: OmH(nEns) double precision :: Omx(nEns) double precision :: Omc(nEns) double precision :: Omaux(nEns) double precision :: OmxDD(nEns) double precision :: OmcDD(nEns) double precision,external :: trace_matrix integer :: ispin,iEns,iBas double precision,allocatable :: nEl(:) double precision,allocatable :: kappa(:) double precision :: E(nEns) double precision :: Om(nEns) double precision,external :: electron_number ! Compute scaling factor for N-centered ensembles allocate(nEl(nEns),kappa(nEns)) nEl(:) = 0d0 do iEns=1,nEns do iBas=1,nBas do ispin=1,nspin nEl(iEns) = nEl(iEns) + occnum(iBas,ispin,iEns) end do end do kappa(iEns) = nEl(iEns)/nEl(1) end do !------------------------------------------------------------------------ ! Kinetic energy !------------------------------------------------------------------------ do ispin=1,nspin do iEns=1,nEns ET(ispin,iEns) = trace_matrix(nBas,matmul(P(:,:,ispin,iEns),T(:,:))) end do end do !------------------------------------------------------------------------ ! Potential energy !------------------------------------------------------------------------ do iEns=1,nEns do ispin=1,nspin EV(ispin,iEns) = trace_matrix(nBas,matmul(P(:,:,ispin,iEns),V(:,:))) end do end do !------------------------------------------------------------------------ ! Individual Hartree energy !------------------------------------------------------------------------ do ispin=1,nspin call unrestricted_hartree_potential(nBas,Pw(:,:,ispin),ERI,J(:,:,ispin)) end do do iEns=1,nEns if(doNcentered) then EH(1,iEns) = kappa(iEns)*trace_matrix(nBas,matmul(P(:,:,1,iEns),J(:,:,1))) EH(2,iEns) = kappa(iEns)*trace_matrix(nBas,matmul(P(:,:,1,iEns),J(:,:,2))) & + kappa(iEns)*trace_matrix(nBas,matmul(P(:,:,2,iEns),J(:,:,1))) EH(3,iEns) = kappa(iEns)*trace_matrix(nBas,matmul(P(:,:,2,iEns),J(:,:,2))) else EH(1,iEns) = trace_matrix(nBas,matmul(P(:,:,1,iEns),J(:,:,1))) EH(2,iEns) = trace_matrix(nBas,matmul(P(:,:,1,iEns),J(:,:,2))) & + trace_matrix(nBas,matmul(P(:,:,2,iEns),J(:,:,1))) EH(3,iEns) = trace_matrix(nBas,matmul(P(:,:,2,iEns),J(:,:,2))) end if end do ! Levy-Zahariev shif for Hartree if(doNcentered) then ! Do I need to scale this term? ! LZH(:) = 0d0 else ! LZH(1) = - 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,1),J(:,:,1))) ! LZH(2) = - 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,1),J(:,:,2))) & ! - 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,2),J(:,:,1))) ! LZH(3) = - 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,2),J(:,:,2))) LZH(1) = - 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,1),J(:,:,1))) & - 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,2),J(:,:,1))) LZH(2) = 0d0 ! print*,- 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,1)+Pw(:,:,2),J(:,:,2))) print*,- 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,1),J(:,:,2))) print*,- 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,2),J(:,:,2))) LZH(3) = - 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,1),J(:,:,2))) - 0.5d0*trace_matrix(nBas,matmul(Pw(:,:,2),J(:,:,2))) print*,LZH(3) end if !------------------------------------------------------------------------ ! Individual exchange energy !------------------------------------------------------------------------ do iEns=1,nEns do ispin=1,nspin call unrestricted_exchange_energy(x_rung,x_DFA,LDA_centered,nEns,wEns,nCC,aCC,nGrid,weight,nBas, & P(:,:,ispin,iEns),FxHF(:,:,ispin),rho(:,ispin,iEns),drho(:,:,ispin,iEns), & Ex(ispin,iEns),Cx_choice,doNcentered) end do end do ! Levy-Zahariev shif for exchange do ispin=1,nspin call unrestricted_exchange_individual_energy(x_rung,x_DFA,LDA_centered,nEns,wEns,nCC,aCC,nGrid,weight,nBas,ERI, & Pw(:,:,ispin),rhow(:,ispin),drhow(:,:,ispin),Cx_choice,doNcentered, & LZx(ispin)) end do !------------------------------------------------------------------------ ! Individual correlation energy !------------------------------------------------------------------------ do iEns=1,nEns call unrestricted_correlation_energy(c_rung,c_DFA,nEns,wEns,nGrid,weight,rho(:,:,iEns),drho(:,:,:,iEns),Ec(:,iEns)) end do ! Levy-Zahariev shif for correlation call unrestricted_correlation_individual_energy(c_rung,c_DFA,LDA_centered,nEns,wEns,nGrid,weight,rhow,drhow,doNcentered,LZc) !------------------------------------------------------------------------ ! Compute auxiliary energies !------------------------------------------------------------------------ call unrestricted_auxiliary_energy(nBas,nEns,eps,occnum,doNcentered,Eaux) !------------------------------------------------------------------------ ! Compute derivative discontinuities !------------------------------------------------------------------------ do ispin=1,nspin call unrestricted_exchange_derivative_discontinuity(x_rung,x_DFA,nEns,wEns,nCC,aCC,nGrid,weight, & rhow(:,ispin),drhow(:,:,ispin),Cx_choice,doNcentered,kappa,ExDD(ispin,:)) end do call unrestricted_correlation_derivative_discontinuity(c_rung,c_DFA,nEns,wEns,nGrid,weight,rhow,drhow,kappa,EcDD) !------------------------------------------------------------------------ ! Total energy !------------------------------------------------------------------------ do iEns=1,nEns E(iEns) = sum(ET(:,iEns)) + sum(EV(:,iEns)) & + sum(EH(:,iEns)) + sum(Ex(:,iEns)) + sum(Ec(:,iEns)) & + sum(LZH(:)) + sum(LZx(:)) + sum(LZc(:)) & + sum(ExDD(:,iEns)) + sum(EcDD(:,iEns)) end do print*,E do iEns=1,nEns E(iEns) = sum(Eaux(:,iEns)) & + sum(LZH(:)) + sum(LZx(:)) + sum(LZc(:)) & + sum(ExDD(:,iEns)) + sum(EcDD(:,iEns)) end do print*,E !------------------------------------------------------------------------ ! Excitation energies !------------------------------------------------------------------------ do iEns=1,nEns Om(iEns) = E(iEns) - E(1) OmH(iEns) = sum(EH(:,iEns)) - sum(EH(:,1)) Omx(iEns) = sum(Ex(:,iEns)) - sum(Ex(:,1)) Omc(iEns) = sum(Ec(:,iEns)) - sum(Ec(:,1)) Omaux(iEns) = sum(Eaux(:,iEns)) - sum(Eaux(:,1)) OmxDD(iEns) = sum(ExDD(:,iEns)) - sum(ExDD(:,1)) OmcDD(iEns) = sum(EcDD(:,iEns)) - sum(EcDD(:,1)) end do !------------------------------------------------------------------------ ! Dump results !------------------------------------------------------------------------ call print_unrestricted_individual_energy(nEns,ENuc,Ew,ET,EV,EH,Ex,Ec,Eaux,ExDD,EcDD,E,Om,Omx,Omc,Omaux,OmxDD,OmcDD) end subroutine unrestricted_individual_energy