[molpro-user] Curves not smooth
Peterson, Kirk
kipeters at wsu.edu
Sat Sep 14 16:34:39 BST 2013
Dear Bhargava,
can you provide a simpler input (and maybe snippets of output) without all the ddr stuff to the list that displays the same problem? Presumably you just have a third state that is encroaching at some distances.
regards,
-Kirk
On Sep 14, 2013, at 6:42 AM, Bhargava Anusuri <bhargava.anusuri at gmail.com<mailto:bhargava.anusuri at gmail.com>> wrote:
Dear molpro users,
I've been computing two-state potential energy curves of same symmetry for Li+ ion and NO system. For some r(NO) values the the second state is not smooth with sharp inflections. I circumvented this problem in some cases by increasing n value in 'state,n;'. But in some cases it still persists. I tried incresing 'nstati' in CI but then the 3rd root is getting involved and CI is not converging. Any help is greatly appreciated. Given below is my input:
***,LiNO+ Diabatization and NACME calculation, noorient and x is removed, rno fixed at 2.4 as in paper
memory,300,m
gthresh,energy=0.32d-6
gprint,orbitals
rli=16.0d0
conv=0.52917725d0
rliang=rli*conv
rnang=1.28d0*conv
roang=-1.12d0*conv
geomtyp=xyz
geometry
3
LiNO+ 15 degrees
Li rliang*sin(15) 0.00000000 rliang*cos(15)
N 0.00000000 0.00000000 rnang
O 0.00000000 0.00000000 roang
end
basis=cc-pVTZ
r=2.8d0
dr=[0,0.0002,-0.0002] !Small displacements for finite difference NACME calculation
reforb1=2140.2 !Orbital dumprecord at reference geometry
refci=6000.2 !MRCI record at reference geometry
savci=6100.2 !MRCI record at displaced geometries
text,compute wavefunction at reference geometry (C2v)
hf;wf,17,1,1;orbital,2100.2
multi;
maxiter,40;
pspace,0.05;
wf,17,1,1;state,2; !X 1A1 and A 1A1 states,optimize two states of symmetry 1
natorb,reforb1 !Save reference orbitals on reforb1
noextra !Dont use extra symmetries
ci;
option,maxit=40 !MRCI at reference geometry
option,maxiti=3000;
!option,nstati=5;
closed,5;
occ,10,3;
wf,17,1,1;state,2; !X 1A1 and A 1A1 states
orbital,reforb1 !Use orbitals from previous CASSCF
save,refci; !Save MRCI wavefunction
Text,Displaced geometries
do i=1,42 !Loop over different r values
data,truncate,savci+1 !truncate dumpfile after reference
reforb=reforb1
do j=1,3 !Loop over small displacements for NACME
rli=r+dr(j) !Set current rh
!--------------------------------------------------------------------
conv=0.52917725d0
rliang=rli*conv
rnang=1.28d0*conv
roang=-1.12d0*conv
geomtyp=xyz
geometry
3
LiNO+ 15 degrees
Li rliang*sin(15) 0.00000000 rliang*cos(15)
N 0.00000000 0.00000000 rnang
O 0.00000000 0.00000000 roang
end
!--------------------------------------------------------------------
multi;
maxiter,40;
pspace,0.7;
wf,17,1,1;state,2; !Wavefunction definition
start,reforb !Starting orbitals
orbital,3140.2+j; !Dumprecord for orbitals
diab,reforb !Generate diabatic orbitals relative to reference geometry
noextra !Dont use extra symmetries
reforb=3141.2 !Use orbitals for j=1 as reference for j=2,3
ci;
option,maxit=40
option,maxiti=6000;
!option,nstati=5;
closed,5;
occ,10,3;
wf,17,1,1;state,2;
orbital,diabatic !Use diabatic orbitals
save,savci+j; !Save MRCI for displaced geometries
eadia=energy !Save adiabatic energies for use in ddr
if(j.eq.1) then
e1(i)=energy(1) !Save adiabatic energies for table printing
e2(i)=energy(2)
end if
ci;trans,savci+j,savci+j; !Compute transition densities at R2+DR(j)
dm,7000.2+j; !Save transition densities on this record
ci;trans,savci+j,refci; !Compute transition densities between R2+DR(j) and R1
dm,7100.2+j; !Save transition densities on this record
ci;trans,savci+j,savci+1; !Compute transition densities between R and R2+DR(j)
dm,7200.2+j; !Save transition densities on this record
ddr
density,7000.2+j,7100.2+j !Densities for <R2+DR||R2+DR> and <R2+DR||R1>
orbital,3140.2+j,2140.2 !Orbitals for <R2+DR||R2+DR> and <R2+DR||R1>
energy,eadia(1),eadia(2) !Adiabatic energies
mixing,1.1,2.1 !Compute mixing angle and diabatic energies
if(j.eq.1) then !Store diabatic energies for R2 (DR(1)=0)
mixci(i)=mixangci(1) !Mixing angle obtained from ci vectors only
h11ci(i)=hdiaci(1) !Diabatic energies obtained from ci vectors only
h21ci(i)=hdiaci(2) !HDIA contains the lower triangle of the diabatic hamiltonian
h22ci(i)=hdiaci(3)
mixtot(i)=mixang(1) !Mixing angle from total overlap (including first-order correction)
h11(i)=hdia(1) !Diabatic energies obtained from total overlap
h21(i)=hdia(2)
h22(i)=hdia(3)
end if
mix(j)=mixang(1) !Store mixing angles for R2+DR(j)
enddo !End loop over j
dchi(i)=(mix(3)-mix(2))/(dr(3)-dr(2))*pi/180 !Finite difference derivative of mixing angle
ddr
density,7201.2,7202.2,7203.2 !Compute NACME using 3-point formula
orbital,3141.2,3142.2,3143.2
states,2.1,1.1
nacmeci(i)=nacme
capr(i)=r
c=2.4
p(i)=c*capr(i)/capr(i)
if(i.lt.7) then
r=r+0.2d0
elseif(i.ge.7).and.(i.lt.19) then
r=r+0.1d0
elseif(i.ge.19).and.(i.lt.33) then
r=r+0.2d0
elseif(i.ge.33).and.(i.lt.37) then
r=r+0.5d0
else
r=r+1.0d0
endif
enddo
{table,p,capr,mixci,mixtot,dchi,nacmeci
Title,Mixing angles and non-adiabatic coupling matrix elements for LiNO+
save,2.4n.tab}
table,p,capr,e1,e2,h11ci,h22ci,h21ci
Title,Diabatic energies for LiNO+, obtained from CI-vectors
!format,'(f10.2,6f14.8)'
!sort,1
{table,p,capr,e1,e2,h11,h22,h21
title,Diabatic energies for LiNO+, obtained from CI-vectors and orbital correction
save,2.4e.tab}
Regards,
Bhargava Anusuri,
C/O Prof. Sanjay Kumar,
Chemistry Dept.,
IIT Madras.
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