[molpro-user] calculating the energy of a degenerate state using mrci reg

[Kirk Peterson]

Alternatively, if you want to keep your full-valence active space, don't close the C 2s orbital (often not a good idea anyway) and don't average in the neutral state. This will also get you degenerate A' and A" states for your cation in multi. Of course then your mrci calcs will be using different orbitals optimized for different states, but hopefully that will not affect your ionization potential all that much in this case.

-Kirk


On Nov 28, 2010, at 7:51 AM, Zork Zou wrote:

> Hi,
>  
> use occ,9,3; in casscf and mrci, you'll get degenerate states.
>  
> wenli
> 
> --- On Fri, 11/26/10, Rajagopala Reddy seelam <srgreddyseelam at yahoo.co.in> wrote:
> 
> From: Rajagopala Reddy seelam <srgreddyseelam at yahoo.co.in>
> Subject: [molpro-user] calculating the energy of a degenerate state using mrci reg
> To: "molpro" <molpro-user at molpro.net>
> Date: Friday, November 26, 2010, 11:13 PM
> 
> Dear Molpro developers and users,
> 
> I am trying to calculate the a degenerate state X2E of ch3f molecule which belongs to c3v point group . Since Molpro deals with only abelian point group, I must resort to a lower abelian point group which is Cs point group. The E irreducible representations in C3v correlates with a' + a" irreps. But the calculated two states are not coming as degenerate. Even when I used additional references also, but I did not succeed in getting them same. Here with I am giving the input for the calculation.
> 
> ***,ionization potential
> memory,100,m
> basis={h=dz,c=cc-pvtz,f=aug-cc-pvtz}
> geomtyp=xyz
> geometry={5
> equilibrium geometry
> c     0.000000    0.000000   -0.636134
> h     0.000000    1.029894   -0.984650
> h    -0.891914   -0.514947   -0.984650
> h     0.891914   -0.514947   -0.984650
> f     0.000000    0.000000    0.752306
> end}
> rhf;occ,7,2;wf,18,1,0;
> multi;occ,10,3;closed,4,0;wf,18,1,0;wf,17,1,1;wf,17,2,1;
> mrci;occ,10,3;closed,4,0;wf,18,1,0;
> mrci;occ,10,3;closed,4,0;wf,17,1,1;ref,2;
> mrci;occ,10,3;closed,4,0;wf,17,2,1;ref,1;
> exit;
> 
> The states x2a' and x2a" should come same, but the energetics are as follows
> 
> x2a'    -139.02151211
> x2a"   -139.02470637
> 
> Thank you for spending your valuable time regarding my query.
>                                                                                                                 regards
>                                                                  S.Rajagopala Reddy
>                                                                                       Prof.Mahapatra lab
>                                                                                       School of Chemistry
>                                                                                   University of Hyderabad
> 
> 
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