PCM with CASSCF/CASPT2

Posted by Ignacio Fdez. Galván on June 09, 2011 at 11:01:40:

I'm trying to do a CASSCF and CASPT2 calculation with PCM. The setup is pretty simple, I believe:

&RASSCF
JobIph
NActElectrons = 12 0 0
Inactive = 35
Ras2 = 11
CIRoot = 5 5 1
RFRoot = 1

&CASPT2
Density
Multistate = 5 1 2 3 4 5
NoMultistate
Imaginary Shift = 0.1
RFPert

(I know I should be doing nonequilibrium calculations too, but let's ignore that for the moment.)

Now, the problem is that the CASSCF energy does not match the "Reference energy" in the CASPT2 calculation, as it normally does:

From RASSCF:
root number 1 E = -476.38215867 a.u.
root number 2 E = -476.20986319 a.u.
root number 3 E = -476.16584916 a.u.
root number 4 E = -476.15815205 a.u.
root number 5 E = -476.14550228 a.u.

From CASPT2:
(1) Reference energy: -476.3626851474
(2) Reference energy: -476.1933455977
(3) Reference energy: -476.1636067674
(4) Reference energy: -476.1672808941
(5) Reference energy: -476.1649758016

As you can see, even the order is different, and this is the "reference energy", not the "total energy". Is this normal? What is the origin of this discrepancy? Are the CASPT2 energies "correct" then?

And last, but not least: is there anyway to see the different PCM contributions to the final energy?

Follow Ups:

Re: PCM with CASSCF/CASPT2 Patrick Kölle 11:46:33 2/17/12 (0)

Post a Followup

Name:
E-Mail:

Subject:

if B is 1s22s22p1, what is Li?

Passfield:

Comments:
: I'm trying to do a CASSCF and CASPT2 calculation with PCM. The setup is pretty simple, I believe: : &RASSCF : JobIph : NActElectrons = 12 0 0 : Inactive = 35 : Ras2 = 11 : CIRoot = 5 5 1 : RFRoot = 1 : &CASPT2 : Density : Multistate = 5 1 2 3 4 5 : NoMultistate : Imaginary Shift = 0.1 : RFPert : (I know I should be doing nonequilibrium calculations too, but let's ignore that for the moment.) : Now, the problem is that the CASSCF energy does not match the "Reference energy" in the CASPT2 calculation, as it normally does: : From RASSCF: : root number 1 E = -476.38215867 a.u. : root number 2 E = -476.20986319 a.u. : root number 3 E = -476.16584916 a.u. : root number 4 E = -476.15815205 a.u. : root number 5 E = -476.14550228 a.u. : From CASPT2: : (1) Reference energy: -476.3626851474 : (2) Reference energy: -476.1933455977 : (3) Reference energy: -476.1636067674 : (4) Reference energy: -476.1672808941 : (5) Reference energy: -476.1649758016 : As you can see, even the order is different, and this is the "reference energy", not the "total energy". Is this normal? What is the origin of this discrepancy? Are the CASPT2 energies "correct" then? : And last, but not least: is there anyway to see the different PCM contributions to the final energy?

[ Follow Ups ] [ Post Followup ] [ Molcas user's WWWBoard ]