[molpro-user] caspt3 excited states

Mintz, Benjamin J. bm0037 at gmail.com
Wed Jan 19 22:25:51 GMT 2011

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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