[molpro-user] caspt3 excited states

[Mintz, Benjamin J.]

Toru,

Using {rs3;state,1,5;options,nstati=6} worked.

Thanks,
Ben Mintz

On Jan 19, 2011, at 8:04 PM, Toru Shiozaki wrote:

> Dear Benjamin,
> In Molpro, the internal part of the wave function is obtained by the Davidson-like CI,
> and if the initial guess vectors have no overlap with the target vector, it will fail
> to converge to the desirable root (the use of the lower symmetry might be
> related in your case).
> 
> I think that the easiest solution to the problem at hand is to use
> {rs3;state,1,5;options,nstati=6}
> which increases the number of roots to be obtained in the internal CI process.
> 
> It might also help if you play with the "pspace" keyword (see the reference sec.20.3.9).
> The Hamiltonian matrix in pspace configurations is diagonalized
> before the first iteration to prepare the initial guess for the internal vectors.
> {rs3;state,1,5;pspace,1.0}  ! Not sure it works... if you don't like the first solution.
> 
> Best wishes,
> Toru
> 
> On Jan 19, 2011, at 11:25 PM, Mintz, Benjamin J. wrote:
> 
>> To users,
>> 
>> I am trying to compute an excited state without symmetry. The excited state that I would like to compute is the 5th excited state.  The multi step gives me the following for the energies
>> 
>> !MCSCF STATE 1.1 Energy             -192.119014929625
>> !MCSCF STATE 2.1 Energy             -192.093454846540
>> !MCSCF STATE 3.1 Energy             -192.058662803146
>> !MCSCF STATE 4.1 Energy             -192.055868714916 
>> !MCSCF STATE 5.1 Energy             -192.028038675647
>> 
>> 
>> The problem is when I try to do the rs3 part.  If I do {rs3;state,1,5}, I get the following for the reference energies
>> 
>> State     Reference Energy
>>  5        -192.00552318
>>  3        -192.05866280
>>  4        -192.05586871
>>  1        -192.11901493
>>  2        -192.09345485
>> 
>> Specifically, the reference energy for the 5th excited state does not match the MCSCF STATE 5.1, and the computation fails to converge.  If I do {rs3;state,1,6}, I get the following
>> 
>> State     Reference Energy
>>  5        -192.02803868
>>  6        -192.00552318
>>  3        -192.05866280
>>  4        -192.05586871
>>  1        -192.11901493
>>  2        -192.09345485
>> 
>> 
>> The reference energy for the 5th excited state now matches the MCSCF STATE 5.1 energy, and the 6th excited state matches the 5th excited state from the {rs3;state,1,6}.  However, I do not want to compute the 6th excited state.   I want the 5th excited state.  Why is the 6th excited state being computed for the 5th excited state when I do {rs3;state,1,5}?  Is there a work around for this problem, or is there a problem in my computation?
>> 
>> Benjamin J. Mintz
>> Research Associate, Postdoctoral
>> Oak Ridge Leadership Computing Facility (OLCF)
>> Oak Ridge National Laboratory
>> Phone: (865) 574-6639
>> Email: mintzbj at ornl.gov
>> Gmail: bm0037 at gmail.com
>> 
>> 
>> 
>> 
>> 
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