***,h2s Diabatization
gprint,orbitals,civector
symmetry,x
orient,noorient !noorient should always be used for diabatization
geometry={
s;
h1,s,r1;
h2,s,r2,h1,theta}
basis=avdz !This basis is too small for real application
r1=2.5 !Reference geometry
theta=[92]
r=[2.50,2.55,2.60] !Displaced geometries
reforb=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)
r2=r1
{hf;occ,9,2;wf,18,2,4;
orbital,2100.2}
{multi;occ,9,2;closed,4,1;
wf,18,2;state,2; !1B1 and 1A2 states
natorb,reforb !Save reference orbitals on reforb
noextra} !Dont use extra symmetries
{ci;occ,9,2;closed,4,1; !MRCI at reference geometry
wf,18,2,0;state,2; !1B1 and 1A2 states
orbital,reforb !Use orbitals from previous CASSCF
save,refci} !Save MRCI wavefunction
Text,Displaced geometries
do i=1,#r !Loop over different r values
data,truncate,savci+1 !truncate dumpfile after reference
r2=r(i) !Set current r2
{multi;occ,9,2;closed,4,1;
wf,18,2,0;state,2; !Wavefunction definition
start,reforb !Starting orbitals
orbital,3140.2; !Dump record for orbitals
diab,reforb !Generate diabatic orbitals relative to reference geometry
noextra} !Dont use extra symmetries
{ci;occ,9,2;closed,4,1;
wf,18,2,0;state,2; !1B1 and 1A2 states
orbital,diabatic !Use diabatic orbitals
save,savci} !Save MRCI for displaced geometries
e1(i)=energy(1) !Save adiabatic energies
e2(i)=energy(2)
{ci;trans,savci,savci !Compute transition densities at R2
dm,7000.2} !Save transition densities on this record
{ci;trans,savci,refci; !Compute transition densities between R2 and R1
dm,7100.2} !Save transition densities on this record
{ddr
density,7000.2,7100.2 !Densities for and
orbital,3140.2,2140.2 !Orbitals for and
energy,e1(i),e2(i) !Adiabatic energies
mixing,1.2,2.2} !Compute mixing angle and diabatic energies
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)
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)
{table,r,e1,e2,h11ci,h22ci,h21ci,mixci
title,Diabatic energies for H2S, obtained from CI-vectors
format,'(f10.2,5f14.8,f12.2)'
sort,1}
{table,r,e1,e2,h11,h22,h21,mixtot
title,Diabatic energies for H2S, obtained from CI-vectors and orbital correction
format,'(f10.2,5f14.8,f12.2)'
sort,1}
enddo !end loop over i