CASSCF PCM excited state optimization

Posted by Brian Solis on August 17, 2012 at 21:58:33:

I wish to perform a geometry optimization in the presence of solvent to an excited state in a state-averaged CASSCF calculation. I currently have an optimized CASSCF PCM structure for the ground state, which I obtained using:

RF-Input
PCM-model
solvent = dichloroethane
End of RF-Input
...
&RASSCF
rlxroot=1

To optimize the molecule to an excited state I added the keyword "rfroot=5" (for S_4) and changed rlxroot=5 in &RASSCF. I also used the JobIph file from the above optimization (jobiph, cirestart) so that my starting orbital guess is appropriate. After the first RASSCF iteration, I get the exact same energies as the ground-state optimized calculation.

Any help would be greatly appreciated. I have successfully performed optimizations with rfroot and noneq (for investigations at the Franck-Condon point), but rfroot seems to not work for the equilibrium case to an excited state.

Thank you,
-Brian.

Follow Ups:

Re: CASSCF PCM excited state optimization Steven 09:25:49 9/19/12 (1)
- Re: CASSCF PCM excited state optimization Brian Solis 21:30:16 10/02/12 (0)

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Comments:
: I wish to perform a geometry optimization in the presence of solvent to an excited state in a state-averaged CASSCF calculation. I currently have an optimized CASSCF PCM structure for the ground state, which I obtained using: : RF-Input : PCM-model : solvent = dichloroethane : End of RF-Input : ... : &RASSCF : rlxroot=1 : : To optimize the molecule to an excited state I added the keyword "rfroot=5" (for S_4) and changed rlxroot=5 in &RASSCF. I also used the JobIph file from the above optimization (jobiph, cirestart) so that my starting orbital guess is appropriate. After the first RASSCF iteration, I get the exact same energies as the ground-state optimized calculation. : Any help would be greatly appreciated. I have successfully performed optimizations with rfroot and noneq (for investigations at the Franck-Condon point), but rfroot seems to not work for the equilibrium case to an excited state. : Thank you, : -Brian.

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