MOLPRO

6 PROGRAM CONTROL 40
6.13.1 Example for computing expectation values
The following job computes dipole and quadrupole moments for H 2 O.
***,h2o properties
geometry={o;h1,o,r;h2,o,r,h1,theta} !Z-matrix geometry input
r=1 ang !bond length
theta=104
!bond angle
gexpec,dm,sm,qm
!compute dipole and quarupole moments
$methods=[hf,multi,ci]
!do hf, casscf, mrci
do i=1,#methods
!loop over methods
$methods(i)
!run energy calculation
e(i)=energy
dip(i)=dmz
!save dipole moment in variable dip
quadxx(i)=qmxx
!save quadrupole momemts
quadyy(i)=qmyy
quadzz(i)=qmzz
smxx(i)=xx
!save second momemts
smyy(i)=yy
smzz(i)=zz
enddo
table,methods,dip,smxx,smyy,smzz !print table of first and second moments
table,methods,e,quadxx,quadyy,quadzz !print table of quadrupole moments
http://www.molpro.net/info/current/examples/h2o_gexpec2.com
This Job produces the following tables
METHODS DIP SMXX SMYY SMZZ
HF 0.82747571 -5.30079792 -3.01408114 -4.20611391
MULTI 0.76285513 -5.29145148 -3.11711397 -4.25941000
CI 0.76868508 -5.32191822 -3.15540500 -4.28542917
METHODS E QUADXX QUADYY QUADZZ
HF -76.02145798 -1.69070039 1.73937477 -0.04867438
MULTI -76.07843443 -1.60318949 1.65831677 -0.05512728
CI -76.23369821 -1.60150114 1.64826869 -0.04676756
6.13.2 Example for computing relativistic corrections
***,ar2
geometry={ar1;ar2,ar1,r}
r=2.5 ang
{hf;
expec,rel,darwin,massv}
e_nrel=energy
show,massv,darwin,erel
dkroll=1
hf;
e_dk=energy
show,massv,darwin,erel
show,e_dk-e_nrel
!geometry definition
!bond distance
!non-relativisitic scf calculation
!compute relativistic correction using Cowan-Griffin operator
!save non-relativistic energy in variable enrel
!show individual contribution and their sum
!use douglas-kroll one-electron integrals
!relativistic scf calculation
!save relativistic scf energy in variable e_dk.
!show mass-velocity and darwin contributions and their sum
!show relativistic correction using Douglas-Kroll
http://www.molpro.net/info/current/examples/ar2_rel.com
This jobs shows at the end the following variables: