[molpro-user] transition dipole moment calculations

Peter Knowles KnowlesPJ at Cardiff.ac.uk
Tue Feb 8 10:41:00 GMT 2011

```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
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