Le jeudi, 27 mar 2003, à 09:01 Europe/Paris, Kalju Kahn a écrit :


Hello,

I am fairly new to molpro and I am not sure if the problem I am having
with cipt2 calculation of the exited state is a result of my limited
understanding of the method or a program bug.  I am running a cipt2
calculation on the third exited state of benzonitrile.  The molecule
has C2v symmetry and the exited state belongs to A1 irreducible
representation.  The A1 ground state calculation is successful and I
can do RS2 calculations in the exited state after using level shifts
around 0.15.  The relevant portion of my cipt2 input looks like this:
--------------------------------
basis,roos(3s2p1d/2s)

hf

multi
occ,15,6,8,2
core,6,0,2,0
closed,15,0,8,0
wf,54,1,0

cipt2
occ,15,6,8,2
core,6,0,2,0
closed,15,0,8,0
wf,54,1,0
maxiter,80,100
state,1,3
refstate,1,3


I suppose that what you've experienced was a variational collapse of the MRPT2 wf of your 3rd exited state during your PT2 calculation.


Try to put :

state,3

instead of :

state,1,3
refstate,1,3

(the three first MRPT2 roots should be calculated at the same time, taking the three first MCSCF roots as refs.)


Best regards,


Benoît


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