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implement energy and gradient in pCCD

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This commit is contained in:
Pierre-Francois Loos 2024-08-18 16:00:46 +02:00
parent 42565f95f1
commit 68826076cc
3 changed files with 142 additions and 61 deletions
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5
src/CC/RCC.f90
View File

@ -1,5 +1,5 @@
subroutine RCC(dotest,doCCD,dopCCD,doDCD,doCCSD,doCCSDT,dodrCCD,dorCCD,docrCCD,dolCCD, &
maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF)
maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,Hc,ERI,ENuc,ERHF,eHF)
! Coupled-cluster module
@ -32,6 +32,7 @@ subroutine RCC(dotest,doCCD,dopCCD,doDCD,doCCSD,doCCSDT,dodrCCD,dorCCD,docrCCD,d
double precision,intent(in) :: ENuc
double precision,intent(in) :: ERHF
double precision,intent(in) :: eHF(nBas)
double precision,intent(in) :: Hc(nBas,nBas)
double precision,intent(in) :: ERI(nBas,nBas,nBas,nBas)
! Local variables
@ -160,7 +161,7 @@ subroutine RCC(dotest,doCCD,dopCCD,doDCD,doCCSD,doCCSDT,dodrCCD,dorCCD,docrCCD,d
if(dopCCD) then
call wall_time(start_CC)
call pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF)
call pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,Hc,ERI,ENuc,ERHF,eHF)
call wall_time(end_CC)
t_CC = end_CC - start_CC

196
src/CC/pCCD.f90
View File

@ -1,4 +1,4 @@
subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF)
subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,Hc,ERI,ENuc,ERHF,eHF)
! pair CCD module
@ -15,10 +15,13 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
integer,intent(in) :: nBas,nC,nO,nV,nR
double precision,intent(in) :: ENuc,ERHF
double precision,intent(in) :: eHF(nBas)
double precision,intent(in) :: Hc(nBas,nBas)
double precision,intent(in) :: ERI(nBas,nBas,nBas,nBas)
! Local variables
integer :: p,q,r,s,t,u
integer :: pq,rs
integer :: i,j,a,b
integer :: nSCF
@ -35,11 +38,12 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
double precision,allocatable :: OVVO(:,:)
double precision,allocatable :: VVVV(:,:)
double precision,allocatable :: yO(:,:),yV(:,:)
double precision,allocatable :: yO(:,:)
double precision,allocatable :: yV(:,:)
double precision,allocatable :: r(:,:)
double precision,allocatable :: t(:,:)
double precision,allocatable :: z(:,:)
double precision,allocatable :: r2(:,:)
double precision,allocatable :: t2(:,:)
double precision,allocatable :: z2(:,:)
double precision,allocatable :: rdm1(:,:)
double precision,allocatable :: rdm2(:,:,:,:)
@ -49,12 +53,16 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
double precision :: tr_1rdm
double precision :: tr_2rdm
integer :: O,V
double precision :: E1,E2
double precision,allocatable :: g(:)
double precision,allocatable :: H(:,:)
integer :: O,V,N
integer :: n_diis
double precision :: rcond
double precision,allocatable :: err_diis(:,:)
double precision,allocatable :: t_diis(:,:)
double precision,allocatable :: z_diis(:,:)
double precision,allocatable :: t2_diis(:,:)
double precision,allocatable :: z2_diis(:,:)
double precision,external :: trace_matrix
! Hello world
@ -68,7 +76,8 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Useful quantities
O = nO - nC
V = nV - NR
V = nV - nR
N = O + V
! Form energy denominator
@ -105,11 +114,11 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Initialization
allocate(t(O,V),r(O,V),yO(O,O),yV(V,V))
allocate(t2(O,V),r2(O,V),yO(O,O),yV(V,V))
! Memory allocation for DIIS
allocate(err_diis(O*V,max_diis),t_diis(O*V,max_diis))
allocate(err_diis(O*V,max_diis),t2_diis(O*V,max_diis))
!------------------------------------------------------------------------
! Compute t ampltiudes
@ -121,8 +130,8 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
EcCC = 0d0
n_diis = 0
t(:,:) = 0d0
t_diis(:,:) = 0d0
t2(:,:) = 0d0
t2_diis(:,:) = 0d0
err_diis(:,:) = 0d0
!------------------------------------------------------------------------
@ -144,23 +153,23 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Form intermediate array
yO(:,:) = matmul(t,transpose(OOVV))
yO(:,:) = matmul(t2,transpose(OOVV))
! Compute residual
r(:,:) = OOVV(:,:) + 2d0*delta_OV(:,:)*t(:,:) &
- 2d0*(2d0*OVOV(:,:) - OVVO(:,:) - OOVV(:,:)*t(:,:))*t(:,:)
r2(:,:) = OOVV(:,:) + 2d0*delta_OV(:,:)*t2(:,:) &
- 2d0*(2d0*OVOV(:,:) - OVVO(:,:) - OOVV(:,:)*t2(:,:))*t2(:,:)
do i=1,O
do a=1,V
do j=1,O
r(i,a) = r(i,a) - 2d0*OOVV(j,a)*t(j,a)*t(i,a) + OOOO(j,i)*t(j,a) + yO(i,j)*t(j,a)
r2(i,a) = r2(i,a) - 2d0*OOVV(j,a)*t2(j,a)*t2(i,a) + OOOO(j,i)*t2(j,a) + yO(i,j)*t2(j,a)
end do
do b=1,V
r(i,a) = r(i,a) - 2d0*OOVV(i,b)*t(i,b)*t(i,a) + VVVV(a,b)*t(i,b)
r2(i,a) = r2(i,a) - 2d0*OOVV(i,b)*t2(i,b)*t2(i,a) + VVVV(a,b)*t2(i,b)
end do
end do
@ -168,15 +177,15 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Check convergence
Conv = maxval(abs(r(:,:)))
Conv = maxval(abs(r2(:,:)))
! Update amplitudes
t(:,:) = t(:,:) - 0.5d0*r(:,:)/delta_OV(:,:)
t2(:,:) = t2(:,:) - 0.5d0*r2(:,:)/delta_OV(:,:)
! Compute correlation energy
EcCC = trace_matrix(V,matmul(transpose(OOVV),t))
EcCC = trace_matrix(V,matmul(transpose(OOVV),t2))
! Dump results
@ -187,7 +196,7 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
if(max_diis > 1) then
n_diis = min(n_diis+1,max_diis)
call DIIS_extrapolation(rcond,nO*nV,nO*nV,n_diis,err_diis,t_diis,-0.5d0*r/delta_OV,t)
call DIIS_extrapolation(rcond,nO*nV,nO*nV,n_diis,err_diis,t2_diis,-0.5d0*r2/delta_OV,t2)
end if
@ -215,15 +224,15 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Deallocate memory
deallocate(err_diis,t_diis)
deallocate(err_diis,t2_diis)
! Memory allocation
allocate(z(O,V))
allocate(z2(O,V))
! Memory allocation for DIIS
allocate(err_diis(O*V,max_diis),z_diis(O*V,max_diis))
allocate(err_diis(O*V,max_diis),z2_diis(O*V,max_diis))
!------------------------------------------------------------------------
! Compute z ampltiudes
@ -232,8 +241,8 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
Conv = 1d0
nSCF = 0
n_diis = 0
z_diis(:,:) = 0d0
n_diis = 0
z2_diis(:,:) = 0d0
err_diis(:,:) = 0d0
!------------------------------------------------------------------------
@ -255,29 +264,25 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Form intermediate array
yO(:,:) = matmul(OOVV,transpose(t))
yV(:,:) = matmul(transpose(OOVV),t)
yO(:,:) = matmul(OOVV,transpose(t2))
yV(:,:) = matmul(transpose(OOVV),t2)
! Compute residual
r(:,:) = OOVV(:,:) + 2d0*delta_OV(:,:)*z(:,:) &
- 2d0*(2d0*OVOV(:,:) - OVVO(:,:) - 2d0*OOVV(:,:)*t(:,:))*z(:,:)
r2(:,:) = OOVV(:,:) + 2d0*delta_OV(:,:)*z2(:,:) &
- 2d0*(2d0*OVOV(:,:) - OVVO(:,:) - 2d0*OOVV(:,:)*t2(:,:))*z2(:,:)
do i=1,O
do a=1,V
do j=1,O
r(i,a) = r(i,a) - 2d0*OOVV(j,a)*t(j,a)*z(i,a) &
- 2d0*OOVV(i,a)*z(j,a)*t(j,a) &
+ OOOO(i,j)*z(j,a) &
+ yO(i,j)*z(j,a)
r2(i,a) = r2(i,a) - 2d0*OOVV(j,a)*t2(j,a)*z2(i,a) - 2d0*OOVV(i,a)*z2(j,a)*t2(j,a) &
+ OOOO(i,j)*z2(j,a) + yO(i,j)*z2(j,a)
end do
do b=1,V
r(i,a) = r(i,a) - 2d0*OOVV(i,b)*t(i,b)*z(i,a) &
- 2d0*OOVV(i,a)*z(i,b)*t(i,b) &
+ VVVV(b,a)*z(i,b) &
+ yV(a,b)*z(i,b)
r2(i,a) = r2(i,a) - 2d0*OOVV(i,b)*t2(i,b)*z2(i,a) - 2d0*OOVV(i,a)*z2(i,b)*t2(i,b) &
+ VVVV(b,a)*z2(i,b) + yV(a,b)*z2(i,b)
end do
end do
@ -285,18 +290,18 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Check convergence
Conv = maxval(abs(r(:,:)))
Conv = maxval(abs(r2(:,:)))
! Update amplitudes
z(:,:) = z(:,:) - 0.5d0*r(:,:)/delta_OV(:,:)
z2(:,:) = z2(:,:) - 0.5d0*r2(:,:)/delta_OV(:,:)
! DIIS extrapolation
if(max_diis > 1) then
n_diis = min(n_diis+1,max_diis)
call DIIS_extrapolation(rcond,O*V,O*V,n_diis,err_diis,z_diis,-0.5d0*r/delta_OV,z)
call DIIS_extrapolation(rcond,O*V,O*V,n_diis,err_diis,z2_diis,-0.5d0*r2/delta_OV,z2)
end if
@ -325,7 +330,7 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Deallocate memory
deallocate(err_diis,z_diis,r)
deallocate(err_diis,z2_diis,r2)
!--------------------------!
! Compute density matrices !
@ -333,13 +338,13 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
allocate(xOO(O,O),xVV(V,V),xOV(O,V))
xOO(:,:) = matmul(t,transpose(z))
xVV(:,:) = matmul(transpose(z),t)
xOV(:,:) = matmul(t,matmul(transpose(z),t))
xOO(:,:) = matmul(t2,transpose(z2))
xVV(:,:) = matmul(transpose(z2),t2)
xOV(:,:) = matmul(t2,matmul(transpose(z2),t2))
! Form 1RDM
allocate(rdm1(O+V,O+V))
allocate(rdm1(N,N))
rdm1(:,:) = 0d0
@ -353,8 +358,8 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Check 1RDM
tr_1rdm = trace_matrix(O+V,rdm1)
write(*,*) ' --> Trace of the 1RDM = ',tr_1rdm
tr_1rdm = trace_matrix(N,rdm1)
write(*,'(A25,F16.10)') ' --> Trace of the 1RDM = ',tr_1rdm
if( abs(dble(2*O) - tr_1rdm) > thresh ) &
write(*,*) ' !!! Your 1RDM seems broken !!! '
@ -362,7 +367,7 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Form 2RM
allocate(rdm2(O+V,O+V,O+V,O+V))
allocate(rdm2(N,N,N,N))
rdm2(:,:,:,:) = 0d0
@ -378,7 +383,7 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
do i=1,O
do a=1,V
rdm2(i,i,O+a,O+a) = 2d0*(t(i,a) + xOV(i,a) - 2d0*t(i,a)*(xVV(a,a) + xOO(i,i) - t(i,a)*z(i,a)))
rdm2(i,i,O+a,O+a) = 2d0*(t2(i,a) + xOV(i,a) - 2d0*t2(i,a)*(xVV(a,a) + xOO(i,i) - t2(i,a)*z2(i,a)))
end do
end do
@ -386,7 +391,7 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
do i=1,O
do a=1,V
rdm2(O+a,O+a,i,i) = 2d0*z(a,i)
rdm2(O+a,O+a,i,i) = 2d0*z2(i,a)
end do
end do
@ -424,7 +429,7 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
do i=1,O
do a=1,V
rdm2(i,O+a,i,O+a) = 4d0*(xVV(a,a) - t(i,a)*z(i,a))
rdm2(i,O+a,i,O+a) = 4d0*(xVV(a,a) - t2(i,a)*z2(i,a))
end do
end do
@ -432,7 +437,7 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
do i=1,O
do a=1,V
rdm2(i,O+a,O+a,i) = - 2d0*(xVV(a,a) - t(i,a)*z(i,a))
rdm2(i,O+a,O+a,i) = - 2d0*(xVV(a,a) - t2(i,a)*z2(i,a))
end do
end do
@ -440,7 +445,7 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
do i=1,O
do a=1,V
rdm2(O+a,i,O+a,i) = 4d0*(xVV(a,a) - t(i,a)*z(i,a))
rdm2(O+a,i,O+a,i) = 4d0*(xVV(a,a) - t2(i,a)*z2(i,a))
end do
end do
@ -448,7 +453,7 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
do i=1,O
do a=1,V
rdm2(O+a,i,i,O+a) = - 2d0*(xVV(a,a) - t(i,a)*z(i,a))
rdm2(O+a,i,i,O+a) = - 2d0*(xVV(a,a) - t2(i,a)*z2(i,a))
end do
end do
@ -460,13 +465,88 @@ subroutine pCCD(dotest,maxSCF,thresh,max_diis,nBas,nC,nO,nV,nR,ERI,ENuc,ERHF,eHF
! Check 2RDM
tr_2rdm = trace_matrix((O+V)**2,rdm2)
write(*,*) ' --> Trace of the 2RDM = ',tr_2rdm
tr_2rdm = trace_matrix(N**2,rdm2)
write(*,'(A25,F16.10)') ' --> Trace of the 2RDM = ',tr_2rdm
if( abs(dble(2*O*(2*O-1)) - tr_2rdm) > thresh ) &
write(*,*) ' !!! Your 2RDM seems broken !!! '
write(*,*)
! Compute electronic energy
E1 = 0d0
E2 = 0d0
do p=1,N
do q=1,N
E1 = E1 + rdm1(p,q)*Hc(p,q)
do r=1,N
do s=1,N
E2 = E2 + rdm2(p,q,r,s)*ERI(p,q,r,s)
end do
end do
end do
end do
E2 = 0.5d0*E2
write(*,'(A25,F16.10)') ' One-electron energy = ',E1
write(*,'(A25,F16.10)') ' Two-electron energy = ',E2
write(*,'(A25,F16.10)') ' Electronic energy = ',E1 + E2
write(*,'(A25,F16.10)') ' Total energy = ',E1 + E2 + ENuc
write(*,*)
! Compute gradient
allocate(g(N**2))
g(:) = 0d0
pq = 0
do p=1,N
do q=1,N
pq = pq + 1
do r=1,N
g(pq) = g(pq) + Hc(r,p)*rdm1(r,q) - Hc(q,r)*rdm1(p,r)
end do
do r=1,N
do s=1,N
do t=1,N
g(pq) = g(pq) + (ERI(r,s,p,t)*rdm2(r,s,q,t) - ERI(q,t,r,s)*rdm2(p,t,r,s))
end do
end do
end do
end do
end do
! Compute Hessian
allocate(H(N**2,N**2))
H(:,:) = 0d0
pq = 0
do p=1,N
do q=1,N
pq = pq + 1
rs = 0
do r=1,N
do s=1,N
rs = rs + 1
end do
end do
end do
end do
! Testing zone
if(dotest) then

2
src/QuAcK/RQuAcK.f90
View File

@ -228,7 +228,7 @@ subroutine RQuAcK(dotest,doRHF,doROHF,dostab,dosearch,doMP2,doMP3,doCCD,dopCCD,d
call wall_time(start_CC)
call RCC(dotest,doCCD,dopCCD,doDCD,doCCSD,doCCSDT,dodrCCD,dorCCD,docrCCD,dolCCD, &
maxSCF_CC,thresh_CC,max_diis_CC,nBas,nC,nO,nV,nR,ERI_MO,ENuc,ERHF,eHF)
maxSCF_CC,thresh_CC,max_diis_CC,nBas,nC,nO,nV,nR,Hc,ERI_MO,ENuc,ERHF,eHF)
call wall_time(end_CC)
t_CC = end_CC - start_CC