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SUBROUTINE DERNVO(COORD,DXYZ)
IMPLICIT DOUBLE PRECISION (A-H,O-Z)
INCLUDE 'SIZES'
DIMENSION COORD(3,*), DXYZ(*)
***********************************************************************
*
* IMPLEMENTATION OF ANALYTICAL FORMULATION FOR OPEN SHELL OR CI,
* VARIABLES FINITE DIFFERENCE METHODS,
* STATISTICAL ESTIMATE OF THE ERRORS,
* BY D. LIOTARD
* LABORATOIRE DE CHIMIE STRUCTURALE
* UNIVERSITE DE PAU ET DES PAYS DE L'ADOUR
* AVENUE DE L'UNIVERSITE, 64000, PAU (FRANCE)
*
*
* MODIFIED BY JJPS TO CONFORM TO MOPAC CONVENTIONS
* (NOTE BY JJPS: PROF. LIOTARD'S TECHNIQUE WORKS. IF THIS
* IMPLEMENTATION DOES NOT WORK, THE REASON IS A FAULT INTRODUCED
* BY JJPS, AND DOES NOT REFLECT ON PROF. LIOTARD'S ABILITY)
*
*
* AS THE WAVE FUNCTION IS NOT VARIATIONALLY OPTIMIZED, I.E.
* HALF-ELECTRON OR CI, THE DERIVATIVES OF THE 1 AND 2-ELECTRON
* INTEGRALS IN A.O. BASIS ARE EVALUATED IN CARTESIAN COORDINATES
* BY A 1 OR 2 POINTS FINITE DIFFERENCE FORMULA AND STORED.
* THUS ONE GETS THE NON-RELAXED (I.E. FROZEN ELECTRONIC CLOUD)
* CONTRIBUTION TO THE FOCK EIGENVALUES AND 2-ELECTRON INTEGRALS IN
* AN M.O. BASIS. THE NON-RELAXED GRADIENT COMES FROM THE
* NON-RELAXED C.I. MATRIX DERIVATIVE (SUBROUTINE DERI1).
* THE DERIVATIVES OF THE M.O. COEFFICIENTS ARE THEN WORKED OUT
* ITERATIVELY (OK FOR BOTH CLOSED SHELLS AND HALF-ELECTRON CASES)
* AND STORED. THUS ONE GETS THE ELECTRONIC RELAXATION CONTRIBUTION TO
* THE FOCK EIGENVALUES AND 2-ELECTRON INTEGRALS IN M.O. BASIS.
* FINALLY THE RELAXATION CONTRIBUTION TO THE C.I. MATRIX DERIVATIVE
* GIVES THE RELAXATION CONTRIBUTION TO THE GRADIENT (ROUTINE DERI2).
*
*
* COORD HOLDS THE CARTESIAN COORDINATES.
* INPUT
* DXYZ NOT DEFINED.
* EXIT
* DXYZ DERIVATIVES OF ENERGY W.R.T CARTESIAN COORDINATES,
* IN KCAL/MOL/ANGSTROM (3 * NUMAT OF THESE)
*
***********************************************************************
C
C NW2 and NW3 should be set to *something*, probably sizes of WORK2
C and WORK3 arrays? Since the code works with NW2 and NW3 set to zero
C by implicit initialization, we can as well do it explicitly.... -P.S.
C
PARAMETER (NW2=0,NW3=0)
COMMON /MOLKST/ NUMAT,NAT(NUMATM),NFIRST(NUMATM),NMIDLE(NUMATM)
1 ,NLAST(NUMATM), NORBS, NELECS,NALPHA,NBETA
2 ,NCLOSE,NOPEN,NDUMY,FRACT
COMMON /GRADNT/ GRAD(MAXPAR),GNORM
COMMON /CIBITS/ NMOS,LAB,NELEC,NBO(3)
COMMON /NUMCAL/ NUMCAL
1 /KEYWRD/ KEYWRD
2 /VECTOR/ C(MORB2),EIGS(MAXORB),CBETA(MORB2)
3,EIGB(MAXORB)
COMMON /FOKMAT/ FDUMY(MPACK), SCALAR(MPACK)
COMMON /NVOMAT/ DIAG(MPACK/2)
COMMON /WORK1 / FMOOFF(NPULAY*4), FMOON(NPULAY*4),
1WORK2(9*NPULAY), WORK3(4*NPULAY)
DIMENSION FBWO(5*MAXPAR)
CHARACTER KEYWRD*241, BLANK*60
DIMENSION DXYZR(MAXPAR), EIGBB(6*MAXPAR)
LOGICAL DEBUG, DCAR, LARGE, RELAXD, FORCE
DATA ICALCN /0/
C
C SELECT THE REQUIRED OPTION AND READ KEYWORDS
C --------------------------------------------
C
IF(ICALCN.NE.NUMCAL) THEN
THROLD=0.08D0
DEBUG = (INDEX(KEYWRD,'DERNVO') .NE. 0)
LARGE = (INDEX(KEYWRD,'LARGE') .NE. 0)
FORCE = (INDEX(KEYWRD,'FORC') .NE. 0)
DCAR = (INDEX(KEYWRD,'FORC') + INDEX(KEYWRD,'PREC') .NE. 0)
IF(DCAR)THROLD=0.004D0
DO 11 I=1,NVAX
11 DXYZR(I)=0.D0
C ACTUAL SIZES FOR C.I. GRADIENT CALCULATION.
NBO(1)=NCLOSE
NBO(2)=NOPEN-NCLOSE
NBO(3)=NORBS-NOPEN
MINEAR=NBO(2)*NBO(1)+NBO(3)*NOPEN
NINEAR=(NMOS*(NMOS+1))/2+1
ICALCN = NUMCAL
ENDIF
C SCALING ROW FACTORS TO SPEED CV OF RELAXATION PROCEDURE.
C# CALL TIMER('BEFORE DERI0')
CALL DERI0 (EIGS,NORBS,SCALAR,DIAG,FRACT,NBO)
C# CALL TIMER('AFTER DERI0')
NVAX=3*NUMAT
C
C BECAUSE DERI2 IS CPU INTENSIVE, AND THE CONTRIBUTION TO THE
C DERVIATIVE DUE TO RELAXATION OF THE ELECTRON CLOUD IS RELATIVELY
C INSENSITIVE TO CHANGES IN GEOMETRY, WHERE POSSIBLE ONLY CALCULATE
C THE DERIVATIVE EVERY 2 CALLS TO DERNVO
C
SUM=0.D0
IF(DCAR)THEN
DO 10 I=1,NVAX
10 DXYZR(I)=0.D0
RELAXD=.FALSE.
ENDIF
DO 20 I=1,NVAX
20 SUM=SUM+ABS(DXYZR(I))
RELAXD=(SUM.GT.1.D-7)
C
C IF DXYZR CONTAINS DATA, USE IT AND FLUSH AFTER USE.
C
ILAST=0
30 IFIRST=ILAST+1
J=2
IF(MIN(NW2,NW3)/MAX(MINEAR,NINEAR).LT.10)J=1
ILAST=MIN(NVAX,ILAST+J)
J=1-MINEAR
K=1-NINEAR
DO 40 I=IFIRST,ILAST
K=K+NINEAR
J=J+MINEAR
C
C NON-RELAXED CONTRIBUTION (FROZEN ELECTRONIC CLOUD) IN DXYZ
C AND NON-RELAXED FOCK MATRICES IN FMOOFF AND FMOON.
C CONTENTS OF F-MO-OFF: OPEN-CLOSED, VIRTUAL-CLOSED, AND VIRTUAL-OPEN
C CONTENTS OF F-MO-ON: CLOSED-CLOSED, OPEN-OPEN AND VIRTUAL-VIRTUAL
C OVER M.O. INDICES
C
C# CALL TIMER('BEFORE DERI1')
CALL DERI1(C,NORBS,COORD,I,CBETA,DXYZ(I),FMOOFF(J),MINEAR
1 ,FMOON(K),WORK2,WORK2(6*MPACK),WORK3)
C# CALL TIMER('AFTER DERI1')
40 CONTINUE
IF(DEBUG)THEN
IF(IFIRST.EQ.1.AND.LARGE)THEN
WRITE(6,*)' CONTENTS OF FMOOFF '
WRITE(6,*)' OPEN-CLOSED'
WRITE(6,'(7X,I3,5I12)')(J,J=NCLOSE+1,NOPEN)
DO 50 I=1,NCLOSE
50 WRITE(6,'(I3,6F12.6)')I,(FMOOFF(J),J=(I-1)*NBO(2)+1,I*NBO(2)
1)
C
C
WRITE(6,*)' VIRTUAL-CLOSED'
K=NCLOSE*NBO(2)
WRITE(6,'(7X,I3,5I12)')(J,J=NOPEN+1,MIN(NOPEN+6,NORBS))
DO 60 I=1,NCLOSE
60 WRITE(6,'(I3,6F12.6)')I,
1 (FMOOFF(J+K),J=(I-1)*NBO(3)+1,MIN(6+(I-1)*NBO(3),I*NBO(3)))
K=NCLOSE*NBO(2)+NBO(3)*NCLOSE
C
C
WRITE(6,*)' VIRTUAL-OPEN'
WRITE(6,'(7X,I3,4I12)')(J,J=NCLOSE+1,NOPEN)
DO 70 I=1,MIN(6,NBO(3))
70 WRITE(6,'(I3,6F12.6)')I+NOPEN,
1 (FMOOFF(J+K),J=(I-1)*NBO(2)+1,MIN((I-1)*NBO(2)+6,I*NBO(2)))
WRITE(6,*)' CONTENTS OF FMOON (ACTIVE-SPACE -- ACTIVE SPACE)
1'
K=(NMOS*(NMOS-1))/2
LL=1
BLANK=' '
DO 80 I=1,NMOS
L=LL+NMOS-I-1
WRITE(6,'(A,5F12.6)')BLANK(:12*I),(FMOON(J),J=LL,L),FMOON
1(K+I)
80 LL=L+1
ENDIF
ENDIF
C COMPUTE THE ELECTRONIC RELAXATION CONTRIBUTION.
C
C DERNVO PROVIDES THE FOLLOWING SCRATCH AREAS TO DERI2: EIGB, WORK2,
C WORK3, FBWO, CBETA. THESE ARE DIMENSIONED ON ENTRY TO DERI2
C WHICH IS WHY THEY ARE NOT DECLARED THERE. THEY ARE NOT USED
C AT ALL IN DERNVO.
C
C# CALL TIMER('BEFORE DERI2')
IF(.NOT.RELAXD)
1 CALL DERI2 (C,EIGS,NORBS,MINEAR,FMOOFF
2 ,FMOON,EIGBB, NINEAR,ILAST-IFIRST+1
3 ,CBETA,WORK2,NW2,DXYZR(IFIRST)
4 ,WORK3,NW3,FBWO,THROLD)
C# CALL TIMER('AFTER DERI2')
IF (ILAST.LT.NVAX) GO TO 30
IF(DEBUG)THEN
SUMX=0.D0
SUMY=0.D0
SUMZ=0.D0
DO 90 I=1,NUMAT
SUMX=SUMX+DXYZ(I*3-2)
SUMY=SUMY+DXYZ(I*3-1)
90 SUMZ=SUMZ+DXYZ(I*3)
WRITE(6,*)' CARTESIAN DERIVATIVES DUE TO FROZEN CORE'
WRITE(6,'('' ATOM X Y Z'')')
DO 100 I=1,NUMAT
100 WRITE(6,'(I4,3F12.7)')I,DXYZ(I*3-2),DXYZ(I*3-1),DXYZ(I*3)
WRITE(6,'(/10X,''RESIDUAL ERROR'')')
WRITE(6,'(4X,3F12.7)')SUMX,SUMY,SUMZ
WRITE(6,*)
SUMX=0.D0
SUMY=0.D0
SUMZ=0.D0
DO 110 I=1,NUMAT
SUMX=SUMX+DXYZR(I*3-2)
SUMY=SUMY+DXYZR(I*3-1)
110 SUMZ=SUMZ+DXYZR(I*3)
WRITE(6,*)' CARTESIAN DERIVATIVES DUE TO RELAXING CORE'
WRITE(6,'('' ATOM X Y Z'')')
DO 120 I=1,NUMAT
120 WRITE(6,'(I4,3F12.7)')I,DXYZR(I*3-2),DXYZR(I*3-1),DXYZR(I*3)
WRITE(6,'(/10X,''RESIDUAL ERROR'')')
WRITE(6,'(4X,3F12.7)')SUMX,SUMY,SUMZ
WRITE(6,*)
ENDIF
DO 130 I=1,NVAX
130 DXYZ(I)=DXYZ(I)+DXYZR(I)
IF(RELAXD)THEN
DO 140 I=1,NVAX
140 DXYZR(I)=0.D0
ENDIF
SUMX=0.D0
SUMY=0.D0
SUMZ=0.D0
DO 150 I=1,NUMAT
SUMX=SUMX+DXYZ(I*3-2)
SUMY=SUMY+DXYZ(I*3-1)
150 SUMZ=SUMZ+DXYZ(I*3)
SUM=MAX(1.D-10,ABS(SUMX)+ABS(SUMY)+ABS(SUMZ))
C
C HERE IS A ROUGH BUT SIMPLE METHOD FOR DEFINING THROLD FOR DERI2
C IT MAY NEED MORE WORK
C
IF(.NOT. FORCE .AND. GNORM .GT. 0.001D0)
1 THROLD=THROLD*SQRT(GNORM/(SUM*100.D0))
THROLD=MIN(2.D0,MAX(0.002D0,THROLD))
IF(DEBUG)THEN
WRITE(6,*)'CARTESIAN DERIVATIVES FROM ANALYTICAL C.I. CALCULATI
1ON'
WRITE(6,'('' ATOM X Y Z'')')
DO 160 I=1,NUMAT
160 WRITE(6,'(I4,3F12.7)')I,DXYZ(I*3-2),DXYZ(I*3-1),DXYZ(I*3)
WRITE(6,'(/10X,''RESIDUAL ERROR'')')
WRITE(6,'(4X,3F12.7)')SUMX,SUMY,SUMZ
WRITE(6,*)
ENDIF
RETURN
END
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