[molpro-user] problem with spin-orbit coupling calculation in molpro-2006

[Alexander Mitrushenkov]

Hi Yuri,

I will submit a bug report and have a look at it as this was my code.

Cheers,

Sasha

-- 
Dr. Alexander Mitrushchenkov
Universität Stuttgart
Institut für Theoretische Chemie
Pfaffenwaldring 55
D-70569 Stuttgart

Tel. +49 (0)711 / 685-64409
Fax  +49 (0)711 / 685-64442
e-mail: sasha at theochem.uni-stuttgart.de

On Friday 01 September 2006 21:29, Yuri Georgievski wrote:
> Hi,
> It seems that there is a problem when one tries to calculate the
> spin-orbit coupling with new version of molpro. This problem appears
> only when the geometry is given in cartesian coordinates. Here is the
> example input:
>
> ***, c2h4+o
> memory,100,M
>
> geomtyp=xyz
> geometry={angstrom
> nosym; noorient
> 7
> rotational dynamics
> C,         0.0000000000,       0.0000000000,      -0.6727675475
> C,         0.0000000000,       0.0000000000,       0.6727675475
> H,         0.0000000000,       0.9347675226,      -1.2426977645
> H,         0.0000000000,      -0.9347675226,      -1.2426977645
> H,         0.0000000000,       0.9347675226,       1.2426977645
> H,         0.0000000000,      -0.9347675226,       1.2426977645
> O, 5, 1, 1
> }
>
> basis=vdz
> {rhf; wf, 24, 1, 2}
> {multi; occ, 13; closed, 10; state, 3}
>
> geometry={angstrom
> nosym; noorient
> 7
> rotational dynamics
> C,         0.0000000000,       0.0000000000,      -0.6727675475
> C,         0.0000000000,       0.0000000000,       0.6727675475
> H,         0.0000000000,       0.9347675226,      -1.2426977645
> H,         0.0000000000,      -0.9347675226,      -1.2426977645
> H,         0.0000000000,       0.9347675226,       1.2426977645
> H,         0.0000000000,      -0.9347675226,       1.2426977645
> O, 15, 1, 1
> }
>
> {multi; occ, 13; closed, 10; state, 3}
> {ci; save, 3010.1; state, 3; noexc}
> lsint
> {ci; hlsmat, ls, 3010.1}
> ---
>
> As a result of this calculation one obtains spin-orbit splitting of 110
> 1/cm while for a stand-alone oxygen it should be 75 1/cm for this basis
> set. If one uses a z-matrix geometry representation the result seems to
> be ok. I tried both Pople and Dunning basis sets and this problem
> appears in all cases.  For previous version of molpro, 2002.6, this
> problem does not exist.
>
> Yuri