4
1
mirror of https://github.com/pfloos/quack synced 2024-12-22 20:35:36 +01:00
This commit is contained in:
Pierre-Francois Loos 2019-03-19 09:30:14 +01:00
parent cf996baa88
commit 60269ea3ce
9 changed files with 467 additions and 103 deletions

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@ -1,9 +1,20 @@
1 3
S 3 1.00
38.3600000 0.0238090
5.7700000 0.1548910
1.2400000 0.4699870
S 1 1.00
0.2976000 1.0000000
P 1 1.00
1.2750000 1.0000000
1 5
S 6 1.00
1264.5857000 0.0019448
189.9368100 0.0148351
43.1590890 0.0720906
12.0986630 0.2371542
3.8063232 0.4691987
1.2728903 0.3565202
S 3 1.00
3.1964631 -0.1126487
0.7478133 -0.2295064
0.2199663 1.1869167
S 1 1.00
0.0823099 1.0000000
P 3 1.00
3.1964631 0.0559802
0.7478133 0.2615506
0.2199663 0.7939723
P 1 1.00
0.0823099 1.0000000

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@ -1,14 +1,14 @@
# HF MOM
T F
# MP2 MP3 MP2-F12
F F F
T T F
# CCD CCSD CCSD(T)
F F F
T F F
# CIS TDHF ADC
F F F
# GF2 GF3
F F
# G0W0 evGW qsGW
T F F
F F F
# MCMP2
F

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@ -1,4 +1,4 @@
# nAt nEl nCore nRyd
1 2 0 0
1 4 0 0
# Znuc x y z
He 0.0 0.0 0.0
Be 0.0 0.0 0.0

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@ -1,9 +1,20 @@
1 3
S 3 1.00
38.3600000 0.0238090
5.7700000 0.1548910
1.2400000 0.4699870
S 1 1.00
0.2976000 1.0000000
P 1 1.00
1.2750000 1.0000000
1 5
S 6 1.00
1264.5857000 0.0019448
189.9368100 0.0148351
43.1590890 0.0720906
12.0986630 0.2371542
3.8063232 0.4691987
1.2728903 0.3565202
S 3 1.00
3.1964631 -0.1126487
0.7478133 -0.2295064
0.2199663 1.1869167
S 1 1.00
0.0823099 1.0000000
P 3 1.00
3.1964631 0.0559802
0.7478133 0.2615506
0.2199663 0.7939723
P 1 1.00
0.0823099 1.0000000

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@ -22,7 +22,7 @@ subroutine CCD(maxSCF,thresh,max_diis,nBas,nEl,ERI,ENuc,ERHF,eHF)
integer :: nV
integer :: nSCF
double precision :: Conv
double precision :: EcMP2
double precision :: EcMP2,EcMP3,EcMP4
double precision :: ECCD,EcCCD
double precision,allocatable :: seHF(:)
double precision,allocatable :: sERI(:,:,:,:)
@ -108,7 +108,7 @@ subroutine CCD(maxSCF,thresh,max_diis,nBas,nEl,ERI,ENuc,ERHF,eHF)
t2(:,:,:,:) = -OOVV(:,:,:,:)/delta_OOVV(:,:,:,:)
EcMP2 = 0.25d0*dot_product(pack(OOVV,.true.),pack(t2,.true.))
write(*,'(1X,A10,1X,F10.6)') 'Ec(MP2) = ',EcMP2
EcMP4 = 0d0
! Initialization
@ -163,6 +163,8 @@ subroutine CCD(maxSCF,thresh,max_diis,nBas,nEl,ERI,ENuc,ERHF,eHF)
EcCCD = 0.25d0*dot_product(pack(OOVV,.true.),pack(t2,.true.))
if(nSCF == 1) EcMP3 = 0.25d0*dot_product(pack(OOVV,.true.),pack(t2 + v/delta_OOVV,.true.))
! Dump results
ECCD = ERHF + EcCCD
@ -190,4 +192,12 @@ subroutine CCD(maxSCF,thresh,max_diis,nBas,nEl,ERI,ENuc,ERHF,eHF)
endif
! Moller-Plesset energies
write(*,*)
write(*,'(1X,A15,1X,F10.6)') 'Ec(MP2) = ',EcMP2
write(*,'(1X,A15,1X,F10.6)') 'Ec(MP3) = ',EcMP3
write(*,'(1X,A15,1X,F10.6)') 'Ec(MP4-SDQ) = ',EcMP4
write(*,*)
end subroutine CCD

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@ -1,78 +0,0 @@
subroutine EOM_CCSD(ispin,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,e,ERI)
! Compute EOM-CCSD excitation energies: see Stanton & Bartlett JCP 98 7029 (1993)
implicit none
include 'parameters.h'
! Input variables
integer,intent(in) :: ispin
integer,intent(in) :: maxSCF
double precision,intent(in) :: thresh
integer,intent(in) :: max_diis
integer,intent(in) :: nBas,nC,nO,nV,nR
double precision,intent(in) :: e(nBas),ERI(nBas,nBas,nBas,nBas)
! Local variables
integer :: nH,nP,nHH,nPP,nSCF,n_diis
double precision :: Conv
double precision,external :: Kronecker_delta
double precision,allocatable :: B_ADC(:,:),X_ADC(:,:),e_ADC(:),SigInf(:,:),G_ADC(:,:)
double precision,allocatable :: db_ERI(:,:,:,:),eOld(:),error_diis(:,:),e_diis(:,:)
integer :: i,j,k,l
integer :: a,b,c,d
integer :: p,q,r,s
integer :: nADC,iADC,jADC
! Hello world
write(*,*)
write(*,*)'***********************************'
write(*,*)'| EOM-CCSD calculation |'
write(*,*)'***********************************'
write(*,*)
! Number of holes
nH = nO
nHH = nH*nH
! Number of particles
nP = nV
nPP = nP*nP
write(*,*) 'Total states: ',nH + nP
write(*,*) 'Hole states: ',nH
write(*,*) 'Particle states: ',nP
! Size of EOM-CCSD matrices
nEOM = nH + nP + nH*nPP + nHH*nP + nHH*nPP
write(*,'(1X,A25,I3,A6,I6)') 'Size of EOM-CCSD matrix: ',nEOM,' x ',nEOM
! Memory allocation
allocate()
! Construct EOM-CCSD matrix
H(:,:) = 0d0
iEOM = 1
jEOM = 1
H(iEOM,jEOM) = ECCSD
do p=1,nO
jADC = jADC + 1
B_ADC(jADC,jADC) = e(p)
enddo
end subroutine EOM_CCSD

237
src/MCQC/UHF.f90 Normal file
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@ -0,0 +1,237 @@
subroutine UHF(maxSCF,thresh,max_diis,guess_type,nBas,nO,nV,S,T,V,Hc,ERI,X,ENuc,EUHF)
! Perform unrestricted Hartree-Fock calculation
implicit none
include 'parameters.h'
! Input variables
integer,intent(in) :: maxSCF
integer,intent(in) :: max_diis
integer,intent(in) :: guess_type
double precision,intent(in) :: thresh
integer,intent(in) :: nBas
integer,intent(in) :: nO(nspin),nV(nspin)
double precision,intent(in) :: S(nBas,nBas)
double precision,intent(in) :: T(nBas,nBas)
double precision,intent(in) :: V(nBas,nBas)
double precision,intent(in) :: Hc(nBas,nBas)
double precision,intent(in) :: X(nBas,nBas)
double precision,intent(in) :: ERI(nBas,nBas,nBas,nBas)
double precision,intent(in) :: ENuc
! Local variables
integer :: nSCF
integer :: nBasSq
integer :: n_diis
double precision :: conv
double precision :: rcond(nspin)
double precision :: ET(nspin)
double precision :: EV(nspin)
double precision :: EJ(nsp)
double precision :: Ex(nspin)
double precision :: Ec(nsp)
double precision :: EUHF
double precision,allocatable :: eps(:,:)
double precision,allocatable :: c(:,:,:)
double precision,allocatable :: cp(:,:,:)
double precision,allocatable :: J(:,:,:)
double precision,allocatable :: F(:,:,:)
double precision,allocatable :: Fp(:,:,:)
double precision,allocatable :: Fx(:,:,:)
double precision,allocatable :: err(:,:,:)
double precision,allocatable :: err_diis(:,:,:)
double precision,allocatable :: F_diis(:,:,:)
double precision,external :: trace_matrix
double precision,allocatable :: P(:,:,:)
integer :: ispin
! Hello world
write(*,*)
write(*,*)'************************************************'
write(*,*)'* Unrestricted Hartree-Fock calculation *'
write(*,*)'************************************************'
write(*,*)
! Useful stuff
nBasSq = nBas*nBas
! Memory allocation
allocate(eps(nBas,nspin),c(nBas,nBas,nspin),cp(nBas,nBas,nspin), &
J(nBas,nBas,nspin),F(nBas,nBas,nspin),Fp(nBas,nBas,nspin), &
Fx(nBas,nBas,nspin),err(nBas,nBas,nspin),P(nBas,nBas,nspin), &
err_diis(nBasSq,max_diis,nspin),F_diis(nBasSq,max_diis,nspin))
! Guess coefficients and eigenvalues
if(guess_type == 1) then
do ispin=1,nspin
F(:,:,ispin) = Hc(:,:)
end do
else if(guess_type == 2) then
do ispin=1,nspin
call random_number(F(:,:,ispin))
end do
end if
! Initialization
nSCF = 0
conv = 1d0
n_diis = 0
F_diis(:,:,:) = 0d0
err_diis(:,:,:) = 0d0
!------------------------------------------------------------------------
! Main SCF loop
!------------------------------------------------------------------------
write(*,*)
write(*,*)'------------------------------------------------------------------------------------------'
write(*,'(1X,A1,1X,A3,1X,A1,1X,A16,1X,A1,1X,A16,1X,A1,1X,A16,1X,A1,1X,A10,1X,A1,1X,A10,1X,A1,1X)') &
'|','#','|','E(KS)','|','Ex(KS)','|','Ec(KS)','|','Conv','|','nEl','|'
write(*,*)'------------------------------------------------------------------------------------------'
do while(conv > thresh .and. nSCF < maxSCF)
! Increment
nSCF = nSCF + 1
! Transform Fock matrix in orthogonal basis
do ispin=1,nspin
Fp(:,:,ispin) = matmul(transpose(X(:,:)),matmul(F(:,:,ispin),X(:,:)))
end do
! Diagonalize Fock matrix to get eigenvectors and eigenvalues
cp(:,:,:) = Fp(:,:,:)
do ispin=1,nspin
call diagonalize_matrix(nBas,cp(:,:,ispin),eps(:,ispin))
end do
! Back-transform eigenvectors in non-orthogonal basis
do ispin=1,nspin
c(:,:,ispin) = matmul(X(:,:),cp(:,:,ispin))
end do
! Compute density matrix
do ispin=1,nspin
P(:,:,ispin) = matmul(c(:,1:nO(ispin),ispin),transpose(c(:,1:nO(ispin),ispin)))
end do
! Build Coulomb repulsion
do ispin=1,nspin
call Coulomb_matrix_AO_basis(nBas,P(:,:,ispin),ERI(:,:,:,:),J(:,:,ispin))
end do
! Compute exchange potential
do ispin=1,nspin
call exchange_matrix_AO_basis(nBas,P(:,:,ispin),ERI(:,:,:,:),Fx(:,:,ispin))
end do
! Build Fock operator
do ispin=1,nspin
F(:,:,ispin) = Hc(:,:) + J(:,:,ispin) + J(:,:,mod(ispin,2)+1) + Fx(:,:,ispin)
end do
! Check convergence
do ispin=1,nspin
err(:,:,ispin) = matmul(F(:,:,ispin),matmul(P(:,:,ispin),S(:,:))) - matmul(matmul(S(:,:),P(:,:,ispin)),F(:,:,ispin))
end do
conv = maxval(abs(err(:,:,:)))
! DIIS extrapolation
n_diis = min(n_diis+1,max_diis)
do ispin=1,nspin
call DIIS_extrapolation(rcond(ispin),nBasSq,nBasSq,n_diis,err_diis(:,:,ispin),F_diis(:,:,ispin),err(:,:,ispin),F(:,:,ispin))
end do
! Reset DIIS if required
if(minval(rcond(:)) < 1d-15) n_diis = 0
!------------------------------------------------------------------------
! Compute UHF energy
!------------------------------------------------------------------------
! Kinetic energy
do ispin=1,nspin
ET(ispin) = trace_matrix(nBas,matmul(P(:,:,ispin),T(:,:)))
end do
! Potential energy
do ispin=1,nspin
EV(ispin) = trace_matrix(nBas,matmul(P(:,:,ispin),V(:,:)))
end do
! Coulomb energy
EJ(1) = 0.5d0*trace_matrix(nBas,matmul(P(:,:,1),J(:,:,1)))
EJ(2) = trace_matrix(nBas,matmul(P(:,:,1),J(:,:,2)))
EJ(3) = 0.5d0*trace_matrix(nBas,matmul(P(:,:,2),J(:,:,2)))
! Exchange energy
do ispin=1,nspin
Ex(ispin) = trace_matrix(nBas,matmul(P(:,:,ispin),Fx(:,:,ispin)))
end do
! Total energy
EUHF = sum(ET(:)) + sum(EV(:)) + sum(EJ(:)) + sum(Ex(:)) + sum(Ec(:))
! Dump results
write(*,'(1X,A1,1X,I3,1X,A1,1X,F16.10,1X,A1,1X,F16.10,1X,A1,1X,F16.10,1X,A1,1X,F10.6,1X,A1,1X)') &
'|',nSCF,'|',EUHF + ENuc,'|',sum(Ex(:)),'|',sum(Ec(:)),'|',conv,'|'
end do
write(*,*)'------------------------------------------------------------------------------------------'
!------------------------------------------------------------------------
! End of SCF loop
!------------------------------------------------------------------------
! Did it actually converge?
if(nSCF == maxSCF) then
write(*,*)
write(*,*)'!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!'
write(*,*)' Convergence failed '
write(*,*)'!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!'
write(*,*)
stop
end if
! Compute final UHF energy
call print_UHF(nBas,nO(:),eps(:,:),c(:,:,:),ENuc,ET(:),EV(:),EJ(:),Ex(:),Ec(:),EUHF)
end subroutine UHF

71
src/MCQC/form_u.f90 Normal file
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@ -0,0 +1,71 @@
subroutine form_u(nO,nV,OOOO,VVVV,OVOV,t2,u)
! Form linear array in CCD
implicit none
! Input variables
integer,intent(in) :: nO,nV
double precision,intent(in) :: t2(nO,nO,nV,nV)
double precision,intent(in) :: OOOO(nO,nO,nO,nO)
double precision,intent(in) :: VVVV(nV,nV,nV,nV)
double precision,intent(in) :: OVOV(nO,nV,nO,nV)
! Local variables
integer :: i,j,k,l
integer :: a,b,c,d
! Output variables
double precision,intent(out) :: u(nO,nO,nV,nV)
u(:,:,:,:) = 0d0
do i=1,nO
do j=1,nO
do a=1,nV
do b=1,nV
do c=1,nV
do d=1,nV
u(i,j,a,b) = u(i,j,a,b) + 0.5d0*VVVV(a,b,c,d)*t2(i,j,c,d)
enddo
enddo
enddo
enddo
enddo
enddo
do i=1,nO
do j=1,nO
do k=1,nO
do l=1,nO
do a=1,nV
do b=1,nV
u(i,j,a,b) = u(i,j,a,b) + 0.5d0*OOOO(k,l,i,j)*t2(k,l,a,b)
enddo
enddo
enddo
enddo
enddo
enddo
do i=1,nO
do j=1,nO
do k=1,nO
do a=1,nV
do b=1,nV
do c=1,nV
u(i,j,a,b) = u(i,j,a,b) - OVOV(k,b,j,c)*t2(i,k,a,c) &
+ OVOV(k,a,j,c)*t2(i,k,b,c) &
- OVOV(k,a,i,c)*t2(j,k,b,c) &
+ OVOV(k,b,i,c)*t2(j,k,a,c)
enddo
enddo
enddo
enddo
enddo
enddo
end subroutine form_u

102
src/MCQC/print_UHF.f90 Normal file
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@ -0,0 +1,102 @@
subroutine print_UHF(nBas,nO,eps,c,ENuc,ET,EV,EJ,Ex,Ec,Ew)
! Print one- and two-electron energies and other stuff for UHF calculation
implicit none
include 'parameters.h'
integer,intent(in) :: nBas
integer,intent(in) :: nO(nspin)
double precision,intent(in) :: eps(nBas,nspin)
double precision,intent(in) :: c(nBas,nBas,nspin)
double precision,intent(in) :: ENuc
double precision,intent(in) :: ET(nspin)
double precision,intent(in) :: EV(nspin)
double precision,intent(in) :: EJ(nsp)
double precision,intent(in) :: Ex(nspin)
double precision,intent(in) :: Ec(nsp)
double precision,intent(in) :: Ew
integer :: HOMO(nspin)
integer :: LUMO(nspin)
double precision :: Gap(nspin)
! HOMO and LUMO
HOMO(:) = nO(:)
LUMO(:) = HOMO(:) + 1
Gap(1) = eps(LUMO(1),1) - eps(HOMO(1),1)
Gap(2) = eps(LUMO(2),2) - eps(HOMO(2),2)
! Dump results
write(*,*)
write(*,'(A60)') '-------------------------------------------------'
write(*,'(A40)') ' Summary '
write(*,'(A60)') '-------------------------------------------------'
write(*,'(A40,1X,F16.10,A3)') ' One-electron energy: ',sum(ET(:)) + sum(EV(:)),' au'
write(*,'(A40,1X,F16.10,A3)') ' One-electron a energy: ',ET(1) + EV(1),' au'
write(*,'(A40,1X,F16.10,A3)') ' One-electron b energy: ',ET(2) + EV(2),' au'
write(*,'(A40,1X,F16.10,A3)') ' Kinetic energy: ',sum(ET(:)),' au'
write(*,'(A40,1X,F16.10,A3)') ' Kinetic a energy: ',ET(1),' au'
write(*,'(A40,1X,F16.10,A3)') ' Kinetic b energy: ',ET(2),' au'
write(*,'(A40,1X,F16.10,A3)') ' Potential energy: ',sum(EV(:)),' au'
write(*,'(A40,1X,F16.10,A3)') ' Potential a energy: ',EV(1),' au'
write(*,'(A40,1X,F16.10,A3)') ' Potential b energy: ',EV(2),' au'
write(*,'(A60)') '-------------------------------------------------'
write(*,'(A40,1X,F16.10,A3)') ' Two-electron a energy: ',sum(EJ(:)) + sum(Ex(:)) + sum(Ec(:)),' au'
write(*,'(A40,1X,F16.10,A3)') ' Two-electron aa energy: ',EJ(1) + Ex(1) + Ec(1),' au'
write(*,'(A40,1X,F16.10,A3)') ' Two-electron ab energy: ',EJ(2) + Ec(2),' au'
write(*,'(A40,1X,F16.10,A3)') ' Two-electron bb energy: ',EJ(3) + Ex(2) + Ec(3),' au'
write(*,'(A40,1X,F16.10,A3)') ' Coulomb energy: ',sum(EJ(:)),' au'
write(*,'(A40,1X,F16.10,A3)') ' Coulomb aa energy: ',EJ(1),' au'
write(*,'(A40,1X,F16.10,A3)') ' Coulomb ab energy: ',EJ(2),' au'
write(*,'(A40,1X,F16.10,A3)') ' Coulomb bb energy: ',EJ(3),' au'
write(*,'(A40,1X,F16.10,A3)') ' Exchange energy: ',sum(Ex(:)),' au'
write(*,'(A40,1X,F16.10,A3)') ' Exchange a energy: ',Ex(1),' au'
write(*,'(A40,1X,F16.10,A3)') ' Exchange b energy: ',Ex(2),' au'
write(*,'(A40,1X,F16.10,A3)') ' Correlation energy: ',sum(Ec(:)),' au'
write(*,'(A40,1X,F16.10,A3)') ' Correlation aa energy: ',Ec(1),' au'
write(*,'(A40,1X,F16.10,A3)') ' Correlation ab energy: ',Ec(2),' au'
write(*,'(A40,1X,F16.10,A3)') ' Correlation bb energy: ',Ec(3),' au'
write(*,'(A60)') '-------------------------------------------------'
write(*,'(A40,1X,F16.10,A3)') ' Electronic energy: ',Ew,' au'
write(*,'(A40,1X,F16.10,A3)') ' Nuclear repulsion: ',ENuc,' au'
write(*,'(A40,1X,F16.10,A3)') ' UHF energy: ',Ew + ENuc,' au'
write(*,'(A60)') '-------------------------------------------------'
write(*,'(A40,F13.6,A3)') ' UHF HOMO a energy:',eps(HOMO(1),1)*HatoeV,' eV'
write(*,'(A40,F13.6,A3)') ' UHF LUMO a energy:',eps(LUMO(1),1)*HatoeV,' eV'
write(*,'(A40,F13.6,A3)') ' UHF HOMOa-LUMOa gap:',Gap(1)*HatoeV,' eV'
write(*,'(A60)') '-------------------------------------------------'
write(*,'(A40,F13.6,A3)') ' UHF HOMO b energy:',eps(HOMO(2),2)*HatoeV,' eV'
write(*,'(A40,F13.6,A3)') ' UHF LUMO b energy:',eps(LUMO(2),2)*HatoeV,' eV'
write(*,'(A40,F13.6,A3)') ' UHF HOMOb-LUMOb gap :',Gap(2)*HatoeV,' eV'
write(*,'(A60)') '-------------------------------------------------'
write(*,*)
! Print results
write(*,'(A50)') '-----------------------------------------'
write(*,'(A50)') 'UHF spin-up orbital coefficients '
write(*,'(A50)') '-----------------------------------------'
call matout(nBas,nBas,c(:,:,1))
write(*,'(A50)') '-----------------------------------------'
write(*,'(A50)') 'UHF spin-down orbital coefficients '
write(*,'(A50)') '-----------------------------------------'
call matout(nBas,nBas,c(:,:,2))
write(*,*)
write(*,'(A50)') '---------------------------------------'
write(*,'(A50)') ' UHF spin-up orbital energies '
write(*,'(A50)') '---------------------------------------'
call matout(nBas,1,eps(:,1))
write(*,*)
write(*,'(A50)') '---------------------------------------'
write(*,'(A50)') ' UHF spin-down orbital energies '
write(*,'(A50)') '---------------------------------------'
call matout(nBas,1,eps(:,2))
write(*,*)
end subroutine print_UHF