[molpro-user] CI vectors, single vs. multiple state calcs

[Seth Olsen]

Oh, and... You say the state energies here are well separated, but the problem may be coming from the higher state. If you ask for more roots, is this state well separated from those above? -Seth

Sent from my iPad

On 19/03/2011, at 0:01, "Terry Frankcombe" <tjf at rsc.anu.edu.au> wrote:

> Hi folks
> 
> I'm doing what one might describe as CAS-CI in a (14,9) active space of
> a large system, using Multi.  The orbitals come from a previous CASSCF
> calculation.  I don't understand the results I get for doing a 2 state
> calculation.
> 
> The two commands (in two different jobs, all other aspects being
> identical) are:
> 
> {CASSCF; occ 67; closed 58; WF 130 1 2; dont orbital}
> {CASSCF; occ 67; closed 58; WF 130 1 2; state 2; dont orbital}
> 
> The jobs run fine.  The ground state energy is identical in each case
> (and identical to the energy from the CASSCF calculation that the
> orbitals come from, as expected).  However, for the CI vectors I get:
> 
> CI vector
> =========
> 
> 222222aa0      0.9713361
> 222220aa2     -0.2062039
> 
> for the single state calc and
> 
> CI vector
> =========
> 
> 222222aa0      0.8989227   0.2567884
> 22222a2a0     -0.2150793   0.6329933
> 2222220aa     -0.2237106   0.4707357
> 22222a0a2      0.0532983  -0.2444110
> 2222202aa      0.0534625  -0.2372961
> 222222a0a      0.0722705  -0.2227077
> 22222abaa     -0.1444124  -0.1890428
> 222220aa2     -0.1682664  -0.0702741
> 22222aa20      0.0920977  -0.1629586
> 22222baaa      0.0944303   0.1467891
> 22222aaab      0.0683397   0.1165439
> 22222aa02     -0.0352542   0.0965585
> 22222a02a      0.0491501   0.0911501
> 222220a2a     -0.0008757   0.0870140
> 22222aaba     -0.0183576  -0.0742902
> 22222a20a     -0.0611334  -0.0626342
> 2222a22a0      0.0012538   0.0506651
> 
> for the 2 state calc.
> 
> Why are the two CI vectors for the ground state so different?
> 
> As I understand things, the CI vector is essentially the eigenvector of
> a matrix which should be the same in both cases.  The energy calculated
> for the second state is well separated.  Can anyone help me understand
> what is going on here?
> 
> Regards
> Terry
> 
> 
> -- 
> Dr. Terry Frankcombe
> Research School of Chemistry, Australian National University
> Ph: (+61) 0417 163 509    Skype: terry.frankcombe
> 
> _______________________________________________
> Molpro-user mailing list
> Molpro-user at molpro.net
> http://www.molpro.net/mailman/listinfo/molpro-user