# [molpro-user] transition dipole moment calculations

Jayashree yfpjaya at gmail.com
Tue Feb 8 15:08:47 GMT 2011

```Yes, the x and y components are non-zero. But being an optically allowed
transition, would not the vertical transition from the X state equilibrium
have a non-zero Z component?

On Tue, Feb 8, 2011 at 4:41 AM, Peter Knowles <KnowlesPJ at cardiff.ac.uk>wrote:

> Surely, as the A state is doublet A_1 and the X state is doublet E, the
> transition dipole moment is non-zero for the E part of the dipole operator,
> ie in the xy plane, just as is calculated?
> Peter
> On 7 Feb 2011, at 22:46, Jayashree wrote:
>
> > Hi all,
> > The transition between X state and A state of methoxy free radical is
> dipole allowed, and I expect that the value of <2.1|DMZ|1.1> to be non-zero
> (in fact, a sizeable number). Instead I find it to be almost zero (of the
> order of 1.0e-8). Here is the input I am using and I would appreciate any
> comments or suggestions for carrying out the transition dipole moment
> calculations between the two states.
> >
> > basis=6-311+G(2d,2p)
> > geometry={Angstrom;
> >       c;
> >       o,c,oc;
> >       h1,c,h1c,o,h1co;
> >       h2,c,h2c,o,h2co,h1,dih1;
> >       h3,c,h3c,o,h3co,h1,dih2}
> > oc=         1.39486910,
> > h1c=         1.08983690,
> > h2c=         1.08983690,
> > h3c=         1.08983690,
> > h1co=       109.89813220,
> > h2co=       109.89813220,
> > h3co=       109.89813220,
> > dih1=       120.00000001,
> > dih2=       239.99999999
> >
> > {uhf;occ,7,2;open,7.1;wf,17,1,1}
> > {casscf;maxiter,40;occ,9,3;closed,5,1;wf,17,1,1; state,1}
> > {rs2;option,nstati=2}
> > geometry={Angstrom;
> >       c;
> >       o,c,oc;
> >       h1,c,h1c,o,h1co;
> >       h2,c,h2c,o,h2co,h1,dih1;
> >       h3,c,h3c,o,h3co,h1,dih2}
> > {casscf;maxiter,40;occ,9,3;closed,5,1;wf,17,2,1; state,1}
> > {rs2;option,nstati=2}
> > {casscf;maxiter,40;occ,9,3;closed,5,1;wf,17,2,1;
> state,1;wf,17,1,1;state,2;tran,dm}
> > {table,trdmx,trdmy,trdmz}
> > {rs2;wf,17,1,1;state,1,2;option,nstati=2}
> >
> > Thanks,
> > --
> > Jayashree
> > _______________________________________________
> > Molpro-user mailing list
> > Molpro-user at molpro.net
> > http://www.molpro.net/mailman/listinfo/molpro-user
>
>

--
Jayashree
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