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egrad_nh3oh.f
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egrad_nh3oh.f
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!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
!
! CARACAL - Ring polymer molecular dynamics and rate constant calculations
! on black-box generated potential energy surfaces
!
! Copyright (c) 2023 by Julien Steffen ([email protected])
! Stefan Grimme ([email protected]) (QMDFF code)
!
! Permission is hereby granted, free of charge, to any person obtaining a
! copy of this software and associated documentation files (the "Software"),
! to deal in the Software without restriction, including without limitation
! the rights to use, copy, modify, merge, publish, distribute, sublicense,
! and/or sell copies of the Software, and to permit persons to whom the
! Software is furnished to do so, subject to the following conditions:
!
! The above copyright notice and this permission notice shall be included in
! all copies or substantial portions of the Software.
!
! THE SOFTWARE IS PROVIDED "AS IS", WITHOUT WARRANTY OF ANY KIND, EXPRESS OR
! IMPLIED, INCLUDING BUT NOT LIMITED TO THE WARRANTIES OF MERCHANTABILITY,
! FITNESS FOR A PARTICULAR PURPOSE AND NONINFRINGEMENT. IN NO EVENT SHALL
! THE AUTHORS OR COPYRIGHT HOLDERS BE LIABLE FOR ANY CLAIM, DAMAGES OR OTHER
! LIABILITY, WHETHER IN AN ACTION OF CONTRACT, TORT OR OTHERWISE, ARISING
! FROM, OUT OF OR IN CONNECTION WITH THE SOFTWARE OR THE USE OR OTHER
! DEALINGS IN THE SOFTWARE.
!
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
! Potential energy routine taken from the POTLIB library:
! R. J. Duchovic, Y. L. Volobuev, G. C. Lynch, A. W. Jasper, D. G. Truhlar, T. C. Allison,
! A. F. Wagner, B. C. Garrett, J. Espinosa-García, and J. C. Corchado, POTLIB,
! https://comp.chem.umn.edu/potlib.
subroutine initialize_NH3OH()
implicit double precision (a-h,o-z)
DOUBLE PRECISION :: r, energy, dvdr
DOUBLE PRECISION CART,ANUZERO
INTEGER NULBL,NFLAG,NASURF,NDER
INTEGER N3ATOM, NATOM, ISURF, JSURF
!
PARAMETER (NATOM=25)
PARAMETER (ISURF = 5)
PARAMETER (JSURF = ISURF*(ISURF+1)/2)
COMMON/USROCM_nh3oh/ PENGYGS,PENGYES(ISURF),
+ PENGYIJ(JSURF),
+ DGSCART(NATOM,3),DESCART(NATOM,3,ISURF),
+ DIJCART(NATOM,3,JSURF)
COMMON/USRICM_nh3oh/ CART(NATOM,3),ANUZERO,
+ NULBL(NATOM),NFLAG(20),
+ NASURF(ISURF+1,ISURF+1),NDER
INTEGER :: init
data init /0/
save init
natoms = 6
nder = 1
nasurf = 0
nasurf(1,1) = 1
nflag(1) = 1
nflag(2) = 1
nflag(3) = 0
nflag(4) = 0
nflag(5) = 0
init = 0
call prepot_nh3oh
init = 1
end subroutine initialize_nh3oh
subroutine egrad_nh3oh(q,Natoms,Nbeads,V,dVdq,info)
implicit double precision (a-h,o-z)
INTEGER :: Natoms, Nbeads
DOUBLE PRECISION :: q(3,Natoms,Nbeads)
DOUBLE PRECISION :: dVdq(3,Natoms,Nbeads), V(Nbeads)
INTEGER :: k
DOUBLE PRECISION :: r, energy, dvdr
DOUBLE PRECISION CART,ANUZERO
INTEGER NULBL,NFLAG,NASURF,NDER
INTEGER N3ATOM, NATOM, ISURF, JSURF
INTEGER :: INFO
!
PARAMETER (NATOM=25)
PARAMETER (ISURF = 5)
PARAMETER (JSURF = ISURF*(ISURF+1)/2)
COMMON/USROCM_nh3oh/ PENGYGS,PENGYES(ISURF),
+ PENGYIJ(JSURF),
+ DGSCART(NATOM,3),DESCART(NATOM,3,ISURF),
+ DIJCART(NATOM,3,JSURF)
COMMON/USRICM_nh3oh/ CART(NATOM,3),ANUZERO,
+ NULBL(NATOM),NFLAG(20),
+ NASURF(ISURF+1,ISURF+1),NDER
INTEGER :: init
data init /0/
save init
natoms = 6
nder = 1
nasurf = 0
nasurf(1,1) = 1
info = 0
nflag(1) = 1
nflag(2) = 1
nflag(3) = 0
nflag(4) = 0
nflag(5) = 0
init = 1
v = 0.d0
dvdq(:,:,:) = 0.d0
dvdr = 0.d0
cart(:,:) = 0.d0
do k = 1, Nbeads
call qtocart_nh3oh(q,Natoms,natom,Nbeads,k,cart)
call pot_nh3oh
V(k) = PENGYGS
do i = 1,3
do j = 1,natoms
dvdq(i,j,k) = dgscart(j,i)
end do
end do
END DO
end subroutine egrad_nh3oh
subroutine qtocart_nh3oh(q0,nat,natom,nb,inb,cart)
implicit none
DOUBLE PRECISION :: q0(3,nat,nb), cart(natom,3)
INTEGER :: i,j,k,inb
INTEGER :: nat, natom,nb
do i= 1,3
do j = 1,nat
cart(j,i) = q0(i,j,inb)
end do
end do
!
return
end subroutine qtocart_nh3oh
c**************************************************************************
C System: NH3OH
C Number of electronic surfaces: 1
C Number of derivatives: 0
C Number of bodies: 6
C Interface: potlib2001
C Common name: NH3OH
C Notes:
C
C References: M. Monge-Palacios, C. Rangel and J. Espinosa-Garcia,
C J.Chem.Phys. 138, 084305 (2013)
SUBROUTINE POT_nh3oh
C
C This potential is written such that:
C
C X(1) - X(3) : X, Y, Z for H1
C X(4) - X(6) : X, Y, Z for N
C X(7) - X(9) : X, Y, Z for H2
C X(10) - X(12) : X, Y, Z for H3
C X(13) - X(15) : X, Y, Z for O (Hb)
C X(16) - X(18) : X, Y, Z for H
C
IMPLICIT DOUBLE PRECISION (A-H,O-Z)
C
CHARACTER*75 REF(5)
C
PARAMETER(N3ATOM = 75)
PARAMETER (ISURF = 5)
PARAMETER (JSURF = ISURF*(ISURF+1)/2)
C
PARAMETER (PI = 3.141592653589793D0)
PARAMETER (NATOM = 25)
C
COMMON/PT1CM_nh3oh/ R(N3ATOM), ENGYGS, DEGSDR(N3ATOM)
COMMON/PT3CM_nh3oh/ EZERO(ISURF+1)
COMMON/PT4CM_nh3oh/ ENGYES(ISURF), DEESDR(N3ATOM,ISURF)
COMMON/PT5CM_nh3oh/ ENGYIJ(JSURF), DEIJDR(N3ATOM,JSURF)
C
COMMON/INFOCM_nh3oh/ CARTNU(NATOM,3),INDEXES(NATOM),
+ IRCTNT,NATOMS,ICARTR,MDER,MSURF,REF
C
COMMON/USROCM_nh3oh/ PENGYGS,PENGYES(ISURF),
+ PENGYIJ(JSURF),
+ DGSCART(NATOM,3),DESCART(NATOM,3,ISURF),
+ DIJCART(NATOM,3,JSURF)
C
COMMON/USRICM_nh3oh/ CART(NATOM,3),ANUZERO,
+ NULBL(NATOM),NFLAG(20),
+ NASURF(ISURF+1,ISURF+1),NDER
c
C
COMMON /POTCM_nh3oh/ nnc,nnb,nnh(4),nno,
+ r0chr,r0chp,w1,w2,d1ch,d3ch,
+ a1ch,b1ch,c1ch,
+ d1hh,d3hh,ahh,
+ r0hhr,r0hhp,w3,w4,
+ r0cb,d1cb,d3cbi,acb,
+ a3s,b3s,aphi,bphi,cphi,rphi,
+ atheta,btheta,ctheta,
+ fch3,hch3,
+ fkinf,ak,bk,aa1,aa2,aa3,aa4,aa5,
+ tau,taunh2,optau,
+ fkh2oeq,alph2o,angh2oeq,
+ a3cb,b3cb,rcbsp
C
C DIMENSION COORD(N3TM),DX(N3TM)
C
common /angles/ theta0(4,4),dtheta0(4,4,4),angh2o(4)
common /bonds/ rcb,rch(4),rbh(4),rno,r0ch,r0hh
common /coords/ tcb(3),tno(3),tch(4,3),tbh(4,3)
common /delta1/ fdelta(4),hdelta(4)
common /delta2/ dfdelta(4,4),dhdelta(4,4)
common /force1/ fk0(4,4),f1(4),dfdc(4,4,4),dfdh(4,4,4),fkh2o(3)
common /fsw1/ a1s,b1s,a2s,b2s
common /ip1/ s1(4),ds1(4),s2(4),ds2(4)
common /ndx/ nc(3),nhb(3),nh(4,3),no(3)
common /opb1/ optheta0(4,4), doptheta0(4,4,4),ppito
common /op1/ s3(4),ds3(4)
common /qpdot_pl/ q(150),pdot(150)
common /switch1/ sphi(4),dsphi(4),stheta(4),dstheta(4)
C
CALL CARTOU_nh3oh
CALL CARTTOR_nh3oh
C
C Changing units from angstrom to bohr and initialize
C
DO 10 I = 1, 18
q(I) = R(I)*0.52918d0
pdot(I)=0.D0
10 CONTINUE
! stop "Hphpi"
c
c calculate relative coordinates and bond lengths
c
en=0.0d0
call coorden_nh3oh
c
c calculate switching functions
c
call switchf_nh3oh
c
c calculate reference angles and their derivatives
c
call refangles_nh3oh
call oprefangles_nh3oh
c
c calculate stretching potential
c
call stretch_nh3oh(vstr)
c
c calculate out of plane bending potential
c
c call opbend(vop)
c
c calculate in plane bending potential
c
call ipbend_nh3oh(vip)
c
c total potential energy is vstr+vop+vip
c
en=vstr+vip
c en=vstr+vop+vip
c
c 0.03812 conversion factor from 10(5) j/mol to hartrees
c
en = en*0.03812D0
ENGYGS = en
c
CALL EUNITZERO_nh3oh
IF(NDER.NE.0) THEN
c
c 0.0201723 conversion factor from 10(5)j/mol/A to hartrees/bohr
c
do i=1,18
DEGSDR(i)=pdot(i)*0.0201723d0
enddo
c write(*,*) "degsdr",degsdr(1:18)
c stop "Hphpi"
c JEG Calculo de derivadas numericas de la energia con
c respecto a las coordenadas
PASO= 1.0D-5
do I=1,18
q(I)=q(I) + PASO
call coorden_nh3oh
call switchf_nh3oh
call refangles_nh3oh
call stretch_nh3oh(vstr)
call ipbend_nh3oh(vip)
en=vstr+vip
en=en*0.03812D0
DEGSDR(I)=(en-ENGYGS)/PASO
DEGSDR(I)=DEGSDR(I)*0.52918d0
q(I)=q(I)-PASO
enddo
CALL RTOCART_nh3oh
CALL DEDCOU_nh3oh
ENDIF
C
return
end
c
c******************************************************
c
subroutine coorden_nh3oh
c
c calculates relative coordinates and bond lengths
c
implicit double precision (a-h,o-z)
C
CHARACTER*75 REF(5)
C
PARAMETER(N3ATOM = 75)
PARAMETER (ISURF = 5)
PARAMETER (JSURF = ISURF*(ISURF+1)/2)
C
PARAMETER (PI = 3.141592653589793D0)
PARAMETER (NATOM = 25)
C
COMMON/PT1CM_nh3oh/ R(N3ATOM), ENGYGS, DEGSDR(N3ATOM)
COMMON/PT3CM_nh3oh/ EZERO(ISURF+1)
COMMON/PT4CM_nh3oh/ ENGYES(ISURF), DEESDR(N3ATOM,ISURF)
COMMON/PT5CM_nh3oh/ ENGYIJ(JSURF), DEIJDR(N3ATOM,JSURF)
C
COMMON/INFOCM_nh3oh/ CARTNU(NATOM,3),INDEXES(NATOM),
+ IRCTNT,NATOMS,ICARTR,MDER,MSURF,REF
C
COMMON/USROCM_nh3oh/ PENGYGS,PENGYES(ISURF),
+ PENGYIJ(JSURF),
+ DGSCART(NATOM,3),DESCART(NATOM,3,ISURF),
+ DIJCART(NATOM,3,JSURF)
C
COMMON/USRICM_nh3oh/ CART(NATOM,3),ANUZERO,
+ NULBL(NATOM),NFLAG(20),
+ NASURF(ISURF+1,ISURF+1),NDER
C
COMMON /POTCM_nh3oh/ nnc,nnb,nnh(4),nno,
+ r0chr,r0chp,w1,w2,d1ch,d3ch,
+ a1ch,b1ch,c1ch,
+ d1hh,d3hh,ahh,
+ r0hhr,r0hhp,w3,w4,
+ r0cb,d1cb,d3cbi,acb,
+ a3s,b3s,aphi,bphi,cphi,rphi,
+ atheta,btheta,ctheta,
+ fch3,hch3,
+ fkinf,ak,bk,aa1,aa2,aa3,aa4,aa5,
+ tau,taunh2,optau,
+ fkh2oeq,alph2o,angh2oeq,
+ a3cb,b3cb,rcbsp
C
C DIMENSION COORD(N3TM),DX(N3TM)
C
common /angles/ theta0(4,4),dtheta0(4,4,4),angh2o(4)
common /bonds/ rcb,rch(4),rbh(4),rno,r0ch,r0hh
common /coords/ tcb(3),tno(3),tch(4,3),tbh(4,3)
common /delta1/ fdelta(4),hdelta(4)
common /delta2/ dfdelta(4,4),dhdelta(4,4)
common /force1/ fk0(4,4),f1(4),dfdc(4,4,4),dfdh(4,4,4),fkh2o(3)
common /fsw1/ a1s,b1s,a2s,b2s
common /ip1/ s1(4),ds1(4),s2(4),ds2(4)
common /ndx/ nc(3),nhb(3),nh(4,3),no(3)
common /opb1/ optheta0(4,4), doptheta0(4,4,4),ppito
common /op1/ s3(4),ds3(4)
common /qpdot_pl/ q(150),pdot(150)
common /switch1/ sphi(4),dsphi(4),stheta(4),dstheta(4)
C
c calculate relative coordinates
c
do ind=1,3
tcb(ind)=q(nc(ind))-q(nhb(ind))
do i=1,3
tch(i,ind)=q(nc(ind))-q(nh(i,ind))
tbh(i,ind)=q(nhb(ind))-q(nh(i,ind))
enddo
enddo
do ind=1,3
tno(ind)=q(no(ind))-q(nhb(ind))
end do
c
c calculate bond lengths
c
rcb=sqrt(tcb(1)*tcb(1)+tcb(2)*tcb(2)+tcb(3)*tcb(3))
rno=sqrt(tno(1)*tno(1)+tno(2)*tno(2)+tno(3)*tno(3))
do i=1,3
rch(i)=sqrt(tch(i,1)*tch(i,1)+tch(i,2)*tch(i,2)+
* tch(i,3)*tch(i,3))
rbh(i)=sqrt(tbh(i,1)*tbh(i,1)+tbh(i,2)*tbh(i,2)+
* tbh(i,3)*tbh(i,3))
enddo
c jcc-2010
argmax = 19.d0
P1 = 1.d0
do i = 1, 3
argp1 = (w1*(rch(i)-w2))
if (argp1.lt.argmax) then
t1tmp = 1 - tanh(argp1)
else
t1tmp = 0.d0
endif
P1 = P1 * t1tmp
enddo
r0ch = P1 * r0chr + (1-P1) * r0chp
c jcc-2010
argmax = 19.d0
P2 = 1.d0
argp2 = (w3*(rno-w4))
if (argp2.lt.argmax) then
t2tmp = 1 - tanh(argp2)
else
t2tmp = 0.d0
endif
P2 = P2 * t2tmp
r0hh = P2 * r0hhr + (1-P2) * r0hhp
return
end
c
c******************************************************
c
c
subroutine refangles_nh3oh
c
c subroutine calculates reference angles for the "in-plane" potential
c
implicit double precision (a-h,o-z)
C
CHARACTER*75 REF(5)
C
PARAMETER(N3ATOM = 75)
PARAMETER (ISURF = 5)
PARAMETER (JSURF = ISURF*(ISURF+1)/2)
C
PARAMETER (PI = 3.141592653589793D0)
PARAMETER (NATOM = 25)
C
COMMON/PT1CM_nh3oh/ R(N3ATOM), ENGYGS, DEGSDR(N3ATOM)
COMMON/PT3CM_nh3oh/ EZERO(ISURF+1)
COMMON/PT4CM_nh3oh/ ENGYES(ISURF), DEESDR(N3ATOM,ISURF)
COMMON/PT5CM_nh3oh/ ENGYIJ(JSURF), DEIJDR(N3ATOM,JSURF)
C
COMMON/INFOCM_nh3oh/ CARTNU(NATOM,3),INDEXES(NATOM),
+ IRCTNT,NATOMS,ICARTR,MDER,MSURF,REF
C
COMMON/USROCM_nh3oh/ PENGYGS,PENGYES(ISURF),
+ PENGYIJ(JSURF),
+ DGSCART(NATOM,3),DESCART(NATOM,3,ISURF),
+ DIJCART(NATOM,3,JSURF)
C
COMMON/USRICM_nh3oh/ CART(NATOM,3),ANUZERO,
+ NULBL(NATOM),NFLAG(20),
+ NASURF(ISURF+1,ISURF+1),NDER
C
COMMON /POTCM_nh3oh/ nnc,nnb,nnh(4),nno,
+ r0chr,r0chp,w1,w2,d1ch,d3ch,
+ a1ch,b1ch,c1ch,
+ d1hh,d3hh,ahh,
+ r0hhr,r0hhp,w3,w4,
+ r0cb,d1cb,d3cbi,acb,
+ a3s,b3s,aphi,bphi,cphi,rphi,
+ atheta,btheta,ctheta,
+ fch3,hch3,
+ fkinf,ak,bk,aa1,aa2,aa3,aa4,aa5,
+ tau,taunh2,optau,
+ fkh2oeq,alph2o,angh2oeq,
+ a3cb,b3cb,rcbsp
C
C DIMENSION COORD(N3TM),DX(N3TM)
C
common /angles/ theta0(4,4),dtheta0(4,4,4),angh2o(4)
common /bonds/ rcb,rch(4),rbh(4),rno,r0ch,r0hh
common /coords/ tcb(3),tno(3),tch(4,3),tbh(4,3)
common /delta1/ fdelta(4),hdelta(4)
common /delta2/ dfdelta(4,4),dhdelta(4,4)
common /force1/ fk0(4,4),f1(4),dfdc(4,4,4),dfdh(4,4,4),fkh2o(3)
common /fsw1/ a1s,b1s,a2s,b2s
common /ip1/ s1(4),ds1(4),s2(4),ds2(4)
common /ndx/ nc(3),nhb(3),nh(4,3),no(3)
common /opb1/ optheta0(4,4), doptheta0(4,4,4),ppito
common /op1/ s3(4),ds3(4)
common /qpdot_pl/ q(150),pdot(150)
common /switch1/ sphi(4),dsphi(4),stheta(4),dstheta(4)
C
C tau=acos(-1.0d0/3.0d0)
C pi=4.0d0*atan(1.0d0)
halfpi=0.5d0*pi
twopi=2.0d0*pi
ppito=(twopi-taunh2)/2.0d0
c
c set diagonal elements to zero
c
do i=1,3
theta0(i,i)=0.0d0
do k=1,4
dtheta0(i,i,k)=0.0d0
enddo
enddo
c
c calculate reference angles
c
theta0(1,2)=tau+(tau-ppito)*(sphi(1)*sphi(2)-1.0d0)
* +(tau-taunh2)*(stheta(3)-1.0d0)
theta0(1,3)=tau+(tau-ppito)*(sphi(1)*sphi(3)-1.0d0)
* +(tau-taunh2)*(stheta(2)-1.0d0)
theta0(2,3)=tau+(tau-ppito)*(sphi(2)*sphi(3)-1.0d0)
* +(tau-taunh2)*(stheta(1)-1.0d0)
c
c calculate the derivatives of theta0(i,j) in terms of rch(k)
c quantity calulated is dtheta0(i,j,k)
c
c derivatives wrt rch(1)
c
dtheta0(1,2,1)=(tau-ppito)*dsphi(1)*sphi(2)
dtheta0(1,3,1)=(tau-ppito)*dsphi(1)*sphi(3)
dtheta0(2,3,1)=(tau-taunh2)*dstheta(1)
c
c derivatives wrt rch(2)
c
dtheta0(1,2,2)=(tau-ppito)*sphi(1)*dsphi(2)
dtheta0(1,3,2)=(tau-taunh2)*dstheta(2)
dtheta0(2,3,2)=(tau-ppito)*dsphi(2)*sphi(3)
c
c derivatives wrt rch(3)
c
dtheta0(1,2,3)=(tau-taunh2)*dstheta(3)
dtheta0(1,3,3)=(tau-ppito)*sphi(1)*dsphi(3)
dtheta0(2,3,3)=(tau-ppito)*sphi(2)*dsphi(3)
c
c fill in the other half of the matrix
c
do i=1,2
do j=i+1,3
theta0(j,i)=theta0(i,j)
do k=1,3
dtheta0(j,i,k)=dtheta0(i,j,k)
enddo
enddo
enddo
return
end
c
c******************************************************
c
c
subroutine oprefangles_nh3oh
c
c subroutine calculates reference angles for the "out-plane" potential
c
implicit double precision (a-h,o-z)
C
CHARACTER*75 REF(5)
C
PARAMETER(N3ATOM = 75)
PARAMETER (ISURF = 5)
PARAMETER (JSURF = ISURF*(ISURF+1)/2)
C
PARAMETER (PI = 3.141592653589793D0)
PARAMETER (NATOM = 25)
C
COMMON/PT1CM_nh3oh/ R(N3ATOM), ENGYGS, DEGSDR(N3ATOM)
COMMON/PT3CM_nh3oh/ EZERO(ISURF+1)
COMMON/PT4CM_nh3oh/ ENGYES(ISURF), DEESDR(N3ATOM,ISURF)
COMMON/PT5CM_nh3oh/ ENGYIJ(JSURF), DEIJDR(N3ATOM,JSURF)
C
COMMON/INFOCM_nh3oh/ CARTNU(NATOM,3),INDEXES(NATOM),
+ IRCTNT,NATOMS,ICARTR,MDER,MSURF,REF
C
COMMON/USROCM_nh3oh/ PENGYGS,PENGYES(ISURF),
+ PENGYIJ(JSURF),
+ DGSCART(NATOM,3),DESCART(NATOM,3,ISURF),
+ DIJCART(NATOM,3,JSURF)
C
COMMON/USRICM_nh3oh/ CART(NATOM,3),ANUZERO,
+ NULBL(NATOM),NFLAG(20),
+ NASURF(ISURF+1,ISURF+1),NDER
C
COMMON /POTCM_nh3oh/ nnc,nnb,nnh(4),nno,
+ r0chr,r0chp,w1,w2,d1ch,d3ch,
+ a1ch,b1ch,c1ch,
+ d1hh,d3hh,ahh,
+ r0hhr,r0hhp,w3,w4,
+ r0cb,d1cb,d3cbi,acb,
+ a3s,b3s,aphi,bphi,cphi,rphi,
+ atheta,btheta,ctheta,
+ fch3,hch3,
+ fkinf,ak,bk,aa1,aa2,aa3,aa4,aa5,
+ tau,taunh2,optau,
+ fkh2oeq,alph2o,angh2oeq,
+ a3cb,b3cb,rcbsp
C
C DIMENSION COORD(N3TM),DX(N3TM)
C
common /angles/ theta0(4,4),dtheta0(4,4,4),angh2o(4)
common /bonds/ rcb,rch(4),rbh(4),rno,r0ch,r0hh
common /coords/ tcb(3),tno(3),tch(4,3),tbh(4,3)
common /delta1/ fdelta(4),hdelta(4)
common /delta2/ dfdelta(4,4),dhdelta(4,4)
common /force1/ fk0(4,4),f1(4),dfdc(4,4,4),dfdh(4,4,4),fkh2o(3)
common /fsw1/ a1s,b1s,a2s,b2s
common /ip1/ s1(4),ds1(4),s2(4),ds2(4)
common /ndx/ nc(3),nhb(3),nh(4,3),no(3)
common /opb1/ optheta0(4,4), doptheta0(4,4,4),ppito
common /op1/ s3(4),ds3(4)
common /qpdot_pl/ q(150),pdot(150)
common /switch1/ sphi(4),dsphi(4),stheta(4),dstheta(4)
C
C pi=4.0d0*atan(1.0d0)
halfpi=0.5d0*pi
twopi=2.0d0*pi
ppito=(twopi-taunh2)/2.0d0
c
c set diagonal elements to zero
c
do i=1,2
optheta0(i,i)=0.0d0
do k=1,3
doptheta0(i,i,k)=0.0d0
enddo
enddo
c
c calculate reference angles
c
optheta0(1,1)=optau+(optau-halfpi)*(sphi(1)
* -1.0d0)+(optau-halfpi)*(stheta(3)-1.0d0)
* +(optau-halfpi)*(stheta(2)-1.0d0)
optheta0(2,2)=optau+(optau-halfpi)*(sphi(2)
* -1.0d0)+(optau-halfpi)*(stheta(3)-1.0d0)
* +(optau-halfpi)*(stheta(1)-1.0d0)
optheta0(3,3)=optau+(optau-halfpi)*(sphi(3)
* -1.0d0)+(optau-halfpi)*(stheta(1)-1.0d0)
* +(optau-halfpi)*(stheta(2)-1.0d0)
c
optheta0(1,2)=optau+(optau-halfpi)*(sphi(1)*sphi(2)
* -1.0d0)+(optau-halfpi)*(stheta(3)-1.0d0)
optheta0(1,3)=optau+(optau-halfpi)*(sphi(1)*sphi(3)
* -1.0d0)+(optau-halfpi)*(stheta(2)-1.0d0)
optheta0(2,3)=optau+(optau-halfpi)*(sphi(2)*sphi(3)
* -1.0d0)+(optau-halfpi)*(stheta(1)-1.0d0)
c
c calculate the derivatives of optheta0(i,j) in terms of rch(k)
c quantity calulated is doptheta0(i,j,k)
c
c derivatives wrt rch(1)
c
doptheta0(1,1,1)=(optau-halfpi)*dsphi(1)
doptheta0(2,2,1)=(optau-halfpi)*dstheta(1)
doptheta0(3,3,1)=(optau-halfpi)*dstheta(1)
c
doptheta0(1,2,1)=(optau-halfpi)*dsphi(1)*
* sphi(2)
doptheta0(1,3,1)=(optau-halfpi)*dsphi(1)*
* sphi(3)
doptheta0(2,3,1)=(optau-halfpi)*
* dstheta(1)
c
c derivatives wrt rch(2)
c
doptheta0(1,1,2)=(optau-halfpi)*dstheta(2)
doptheta0(2,2,2)=(optau-halfpi)*dsphi(2)
doptheta0(3,3,2)=(optau-halfpi)*dstheta(2)
c
doptheta0(1,2,2)=(optau-halfpi)*sphi(1)*
* dsphi(2)
doptheta0(1,3,2)=(optau-halfpi)*
* dstheta(2)
doptheta0(2,3,2)=(optau-halfpi)*dsphi(2)*
* sphi(3)
c
c derivatives wrt rch(3)
c
c
doptheta0(1,1,3)=(optau-halfpi)*dstheta(3)
doptheta0(2,2,3)=(optau-halfpi)*dstheta(3)
doptheta0(3,3,3)=(optau-halfpi)*dsphi(3)
c
doptheta0(1,2,3)=(optau-halfpi)*
* dstheta(3)
doptheta0(1,3,3)=(optau-halfpi)*sphi(1)*
* dsphi(3)
doptheta0(2,3,3)=(optau-halfpi)*sphi(2)*
* dsphi(3)
c
c
c fill in the other half of the matrix
c
do i=1,2
do j=i+1,3
optheta0(j,i)=optheta0(i,j)
do k=1,3
doptheta0(j,i,k)=doptheta0(i,j,k)
enddo
enddo
enddo
return
end
c
c******************************************************
c
c
subroutine stretch_nh3oh(vstr)
c
c subroutine to calculate leps-type stretching potential and its
c derivatives
c
implicit double precision (a-h,o-z)
C
CHARACTER*75 REF(5)
C
PARAMETER(N3ATOM = 75)
PARAMETER (ISURF = 5)
PARAMETER (JSURF = ISURF*(ISURF+1)/2)
C
PARAMETER (PI = 3.141592653589793D0)
PARAMETER (NATOM = 25)
C
COMMON/PT1CM_nh3oh/ R(N3ATOM), ENGYGS, DEGSDR(N3ATOM)
COMMON/PT3CM_nh3oh/ EZERO(ISURF+1)
COMMON/PT4CM_nh3oh/ ENGYES(ISURF), DEESDR(N3ATOM,ISURF)
COMMON/PT5CM_nh3oh/ ENGYIJ(JSURF), DEIJDR(N3ATOM,JSURF)
C
COMMON/INFOCM_nh3oh/ CARTNU(NATOM,3),INDEXES(NATOM),
+ IRCTNT,NATOMS,ICARTR,MDER,MSURF,REF
C
COMMON/USROCM_nh3oh/ PENGYGS,PENGYES(ISURF),
+ PENGYIJ(JSURF),
+ DGSCART(NATOM,3),DESCART(NATOM,3,ISURF),
+ DIJCART(NATOM,3,JSURF)
C
COMMON/USRICM_nh3oh/ CART(NATOM,3),ANUZERO,
+ NULBL(NATOM),NFLAG(20),
+ NASURF(ISURF+1,ISURF+1),NDER
C
COMMON /POTCM_nh3oh/ nnc,nnb,nnh(4),nno,
+ r0chr,r0chp,w1,w2,d1ch,d3ch,
+ a1ch,b1ch,c1ch,
+ d1hh,d3hh,ahh,
+ r0hhr,r0hhp,w3,w4,
+ r0cb,d1cb,d3cbi,acb,
+ a3s,b3s,aphi,bphi,cphi,rphi,
+ atheta,btheta,ctheta,
+ fch3,hch3,
+ fkinf,ak,bk,aa1,aa2,aa3,aa4,aa5,
+ tau,taunh2,optau,
+ fkh2oeq,alph2o,angh2oeq,
+ a3cb,b3cb,rcbsp
C
C DIMENSION COORD(N3TM),DX(N3TM)
C
common /angles/ theta0(4,4),dtheta0(4,4,4),angh2o(4)
common /bonds/ rcb,rch(4),rbh(4),rno,r0ch,r0hh
common /coords/ tcb(3),tno(3),tch(4,3),tbh(4,3)
common /delta1/ fdelta(4),hdelta(4)
common /delta2/ dfdelta(4,4),dhdelta(4,4)
common /force1/ fk0(4,4),f1(4),dfdc(4,4,4),dfdh(4,4,4),fkh2o(3)
common /fsw1/ a1s,b1s,a2s,b2s
common /ip1/ s1(4),ds1(4),s2(4),ds2(4)
common /ndx/ nc(3),nhb(3),nh(4,3),no(3)
common /opb1/ optheta0(4,4), doptheta0(4,4,4),ppito
common /op1/ s3(4),ds3(4)
common /qpdot_pl/ q(150),pdot(150)
common /switch1/ sphi(4),dsphi(4),stheta(4),dstheta(4)
C
dimension vqch(4),vjch(4),vqbh(4),vjbh(4),vq(4),vj(4),
* achdc(3),achdh(4,3)
c
c calculate avergage bond length for the nh3 moiety
c
rav=(rch(1)+rch(2)+rch(3))/3.0d0
c
c initialise:
c
vstr=0.0d0
c
texp = exp(-(4.d0*(rav-rcbsp)/b3cb)**4.d0)
d3cb = (d3cbi-a3cb) + a3cb * texp
c dd3cb = -4.d0*a3cb*texp*(rav-rcbsp)**3.d0*(4.d0/b3cb)**4.d0
c ach:
c
c in double precision tanh(19.0d0)=1.0d0 and we put the if statement
c in to avoid overflow/underflow errors
c
arga=c1ch*(rav-r0ch)
if(arga.lt.19.0d0)then
ach=a1ch+b1ch*(tanh(arga)+1.0d0)*0.5d0
dumach=b1ch*c1ch/(2.0d0*cosh(arga)**2)
else
ach=a1ch+b1ch
dumach=0.0d0
endif
c
c calculate singlet: e1, triplet: e3 energies and vq and vj
c terms for each bond
c
e1=d1cb*(exp(-2.0d0*acb*(rcb-r0cb))-2.0d0*exp(-acb*(rcb-r0cb)))
e3=d3cb*(exp(-2.0d0*acb*(rcb-r0cb))+2.0d0*exp(-acb*(rcb-r0cb)))
vqcb=(e1+e3)*0.5d0
vjcb=(e1-e3)*0.5d0
c O-H new term (simple morse term)
c
dt=(rno-r0hh)
expterm=exp(-ahh*dt)
vno=d1hh*(1.d0-expterm)**2.d0
do i=1,3
e1=d1ch*(exp(-2.0d0*ach*(rch(i)-r0ch))
* -2.0d0*exp(-ach*(rch(i)-r0ch)))
e3=d3ch*(exp(-2.0d0*ach*(rch(i)-r0ch))
* +2.0d0*exp(-ach*(rch(i)-r0ch)))
vqch(i)=(e1+e3)*0.5d0
vjch(i)=(e1-e3)*0.5d0
e1=d1hh*(exp(-2.0d0*ahh*(rbh(i)-r0hh))
* -2.0d0*exp(-ahh*(rbh(i)-r0hh)))
e3=d3hh*(exp(-2.0d0*ahh*(rbh(i)-r0hh))
* +2.0d0*exp(-ahh*(rbh(i)-r0hh)))
vqbh(i)=(e1+e3)*0.5d0
vjbh(i)=(e1-e3)*0.5d0
c
c calculate 3 body potential
c
vq(i)=vqch(i)+vqcb+vqbh(i)
vj(i)=-sqrt(((vjch(i)-vjcb)**2+(vjcb-vjbh(i))**2
* +(vjbh(i)-vjch(i))**2)*0.5d0)
vstr=vstr+vq(i)+vj(i)
enddo
c
vstr=vstr+vno
c
c partial derivatives
c first we need the derivative of ach:
c
do ind=1,3
achdc(ind)=dumach*(tch(1,ind)/rch(1)+tch(2,ind)/rch(2)
* +tch(3,ind)/rch(3))/3.0d0
do i=1,3
achdh(i,ind)=-dumach*tch(i,ind)/rch(i)/3.0d0
enddo
enddo
dumqcb=-acb*((d1cb+d3cb)*exp(-2.0d0*acb*(rcb-r0cb))-
* (d1cb-d3cb)*exp(-acb*(rcb-r0cb)))/rcb
c
c calculate cartesian derivatives:
c looping over ch(i) and bh(i)
c
do i=1,3
dumqbh=-ahh*((d1hh+d3hh)*exp(-2.0d0*ahh*(rbh(i)-r0hh))-
* (d1hh-d3hh)*exp(-ahh*(rbh(i)-r0hh)))/rbh(i)
factj=0.5d0/vj(i)
dumjcb=-acb*((d1cb-d3cb)*exp(-2.0d0*acb*(rcb-r0cb))
* -(d1cb+d3cb)*exp(-acb*(rcb-r0cb)))*factj/rcb
dumjbh=-ahh*((d1hh-d3hh)*exp(-2.0d0*ahh*(rbh(i)-r0hh))
* -(d1hh+d3hh)*exp(-ahh*(rbh(i)-r0hh)))*factj/rbh(i)
do ind=1,3
c
c deriv wrt hb:
c
pdot(nhb(ind))=pdot(nhb(ind))
* -tcb(ind)*dumqcb+tbh(i,ind)*dumqbh
* +(vjch(i)-vjcb)*(dumjcb*tcb(ind))
* +(vjcb-vjbh(i))*(-dumjcb*tcb(ind)-dumjbh*tbh(i,ind))
* +(vjbh(i)-vjch(i))*dumjbh*tbh(i,ind)
c
c dvqch(i)/dc
c
dumqch=-(ach*tch(i,ind)/rch(i)+achdc(ind)*(rch(i)-r0ch))
* *((d1ch+d3ch)*exp(-2.0d0*ach*(rch(i)-r0ch))
* -(d1ch-d3ch)*exp(-ach*(rch(i)-r0ch)))
pdot(nc(ind))=pdot(nc(ind))+dumqch+tcb(ind)*dumqcb
c
c dvqch(i)/dh(i)
c
dumqhi=(ach*tch(i,ind)/rch(i)-achdh(i,ind)*(rch(i)-r0ch))
* *((d1ch+d3ch)*exp(-2.0d0*ach*(rch(i)-r0ch))
* -(d1ch-d3ch)*exp(-ach*(rch(i)-r0ch)))
pdot(nh(i,ind))=pdot(nh(i,ind))+dumqhi-tbh(i,ind)*dumqbh
c
c dvjch(i)/dc
c
dumjch=-(ach*tch(i,ind)/rch(i)+achdc(ind)*(rch(i)-r0ch))
* *((d1ch-d3ch)*exp(-2.0d0*ach*(rch(i)-r0ch))
* -(d1ch+d3ch)*exp(-ach*(rch(i)-r0ch)))*factj
c
c dvj(i)/dnc(ind)
c
pdot(nc(ind))=pdot(nc(ind))
* +(vjch(i)-vjcb)*(dumjch-dumjcb*tcb(ind))
* +(vjcb-vjbh(i))*dumjcb*tcb(ind)
* -(vjbh(i)-vjch(i))*dumjch
c
c dvjch(i)/dh(i)
c
dumjhi=(ach*tch(i,ind)/rch(i)-achdh(i,ind)*(rch(i)-r0ch))
* *((d1ch-d3ch)*exp(-2.0d0*ach*(rch(i)-r0ch))
* -(d1ch+d3ch)*exp(-ach*(rch(i)-r0ch)))*factj
c
c dvj(i)/dnh(i,ind)
c
pdot(nh(i,ind))=pdot(nh(i,ind))
* +(vjch(i)-vjcb)*dumjhi
* +(vjcb-vjbh(i))*dumjbh*tbh(i,ind)
* +(vjbh(i)-vjch(i))*(-dumjbh*tbh(i,ind)-dumjhi)
c
c dv(i)/dh(j)
c
do k=1,2
j=i+k
if(j.gt.3)j=j-3
dumqhj=-achdh(j,ind)*(rch(i)-r0ch)
* *((d1ch+d3ch)*exp(-2.0d0*ach*(rch(i)-r0ch))
* -(d1ch-d3ch)*exp(-ach*(rch(i)-r0ch)))
dumjhj=-achdh(j,ind)*(rch(i)-r0ch)
* *((d1ch-d3ch)*exp(-2.0d0*ach*(rch(i)-r0ch))
* -(d1ch+d3ch)*exp(-ach*(rch(i)-r0ch)))*factj
pdot(nh(j,ind))=pdot(nh(j,ind))+dumqhj
* +(vjch(i)-vjcb)*dumjhj
* -(vjbh(i)-vjch(i))*dumjhj
enddo
enddo
enddo
return
end
c
c******************************************************
c
c
subroutine opbend_nh3oh(vop)
c
c subroutine calculates symmetrized vop potential and derivatives
c
implicit double precision (a-h,o-z)
C
CHARACTER*75 REF(5)
C
PARAMETER(N3ATOM = 75)
PARAMETER (ISURF = 5)
PARAMETER (JSURF = ISURF*(ISURF+1)/2)
C
PARAMETER (PI = 3.141592653589793D0)
PARAMETER (NATOM = 25)
C
COMMON/PT1CM_nh3oh/ R(N3ATOM), ENGYGS, DEGSDR(N3ATOM)
COMMON/PT3CM_nh3oh/ EZERO(ISURF+1)
COMMON/PT4CM_nh3oh/ ENGYES(ISURF), DEESDR(N3ATOM,ISURF)
COMMON/PT5CM_nh3oh/ ENGYIJ(JSURF), DEIJDR(N3ATOM,JSURF)
C
COMMON/INFOCM_nh3oh/ CARTNU(NATOM,3),INDEXES(NATOM),
+ IRCTNT,NATOMS,ICARTR,MDER,MSURF,REF
C
COMMON/USROCM_nh3oh/ PENGYGS,PENGYES(ISURF),
+ PENGYIJ(JSURF),
+ DGSCART(NATOM,3),DESCART(NATOM,3,ISURF),
+ DIJCART(NATOM,3,JSURF)
C
COMMON/USRICM_nh3oh/ CART(NATOM,3),ANUZERO,
+ NULBL(NATOM),NFLAG(20),
+ NASURF(ISURF+1,ISURF+1),NDER
C
COMMON /POTCM_nh3oh/ nnc,nnb,nnh(4),nno,
+ r0chr,r0chp,w1,w2,d1ch,d3ch,
+ a1ch,b1ch,c1ch,
+ d1hh,d3hh,ahh,
+ r0hhr,r0hhp,w3,w4,
+ r0cb,d1cb,d3cbi,acb,
+ a3s,b3s,aphi,bphi,cphi,rphi,
+ atheta,btheta,ctheta,
+ fch3,hch3,
+ fkinf,ak,bk,aa1,aa2,aa3,aa4,aa5,
+ tau,taunh2,optau,
+ fkh2oeq,alph2o,angh2oeq,
+ a3cb,b3cb,rcbsp
C
C DIMENSION COORD(N3TM),DX(N3TM)
C
common /angles/ theta0(4,4),dtheta0(4,4,4),angh2o(4)
common /bonds/ rcb,rch(4),rbh(4),rno,r0ch,r0hh
common /coords/ tcb(3),tno(3),tch(4,3),tbh(4,3)
common /delta1/ fdelta(4),hdelta(4)
common /delta2/ dfdelta(4,4),dhdelta(4,4)
common /force1/ fk0(4,4),f1(4),dfdc(4,4,4),dfdh(4,4,4),fkh2o(3)
common /fsw1/ a1s,b1s,a2s,b2s
common /ip1/ s1(4),ds1(4),s2(4),ds2(4)
common /ndx/ nc(3),nhb(3),nh(4,3),no(3)
common /opb1/ optheta0(4,4), doptheta0(4,4,4),ppito
common /op1/ s3(4),ds3(4)
common /qpdot_pl/ q(150),pdot(150)
common /switch1/ sphi(4),dsphi(4),stheta(4),dstheta(4)
C
double precision norma
dimension sumd2(4),sumd4(4)
dimension in(3),a(3),b(3),axb(3),c(4,3),argd(4)
c
c
vop=0.0d0
c
c calculate force constants and their derivatives