[molpro-user] two questions: freq for CASSCF and gradients for QCISD(T)

[Jayashree]

The CPMCSCF is best used when you are dealing with state-averaged orbitals,
like it says in the manual. You seem to be only doing a ground state
calculation, as far as I can see, and CPMCSCF seems unnecessary. You might
want to compare the geometries, basis sets and rotational constants closely
between the molpro and gaussian input to make sure you are looking at the
same calculation. Often in CASSCF, you want to be careful about exactly what
the active space actually is between the two inputs.
Cheers,
Jayashree

>
>
> Today's Topics:
>
>   1. two questions: freq for CASSCF and gradients for  QCISD(T)
>      (eurisco1 at pochta.ru)
>   2. Re: wrong PBE0 energies (Fred Manby)
>
>
> ----------------------------------------------------------------------
>
> Message: 1
> Date: Sun, 22 Nov 2009 15:14:09 +0300
> From: eurisco1 at pochta.ru
> Subject: [molpro-user] two questions: freq for CASSCF and gradients
>        for     QCISD(T)
> To: molpro-user at molpro.net
> Message-ID: <1f8acfcaf3515a5f32861e7e19cc5370771791d8 at www.pochta.ru>
> Content-Type: text/plain; charset="koi8-r"
>
>
>
>
>
>
> Dear Molpro Users and Developers,
>
>
> Would you allow me to address to you
> necessary questions:
>
>
>
> I have calculated frequencies
>        (numerically) as well as analytically by using routes on Version
>        2008.1 linked 05 Sep 2008 (trial) at the level CAS(10,10)/cc-pVDZ
>
>
>
> First input:
>
>
> geomtyp=xyz
>
>
> geometry={
>
>  6
>
>
>
>
>
>  my molecule _xyz
>
> }
>
>
> basis=VdZ
>
>
> {hf;wf,46,1,0,0}
>
> {multi;occ,28;closed,18;wf,46,1,0,0;cpmcscf,hess}
>
> {frequencies}                   !do
>
>
> ---
>
>
> Second input:
>
> geomtyp=xyz
>
>
> geometry={
>
>  6
>
>
>
>
>
> my molecule _xyz
>
> }
>
>
> basis=VdZ
>
>
> {hf;wf,46,1,0,0}
>
> {multi;occ,28;closed,18;wf,46,1,0,0}
>
> {frequencies;
>
>
> print,low,img;}                   !do
>
> and I have always observed only real
> frequencies (which were slightly  different). But if I used Gaussian
> (both 03 and 09) to calculate (numerically) frequencies I observed
> only one imag. (~100i) frequency (I performed IRC and achieved both
> valleys).
>
>
>
>
> Why I got two different results? How
> can I treat this situation?
>
>
>
> In the Molpro manual states that
>        analytical gradients are available
>        for qcisd(t). I have tested simple input
>
>
>
> ! $Revision: 2008.1
>
>
> ***,h2o                   !A title
>
> memory,150,m
>
> r=2.5,theta=120
>
> geometry={o;
>
>          h1,O,r;
>
>          h2,O,r,H1,theta
>
> }
>
>
> basis=vdz
>
>
> rhf
>
> rqcisd(t)
>
>
> optg
>
>
>
>
>
> but I have observed only messages about
> numerical calculations of gradients
>
> Numerical gradient completed.
> CPU-time:     0.75 sec, Elapsed:     2.50 sec
>
>
> What is wrong in my input? Are
> analytical gradients available for geometry optimizations if qcisd(t)
> method is used for calculation of energy?
>
> Sincerely,
>
>
> PhD student Oleg B. Gadzhiev
>
>
> ps: I have downloaded molpro 5 days
> ago.
>
>
>
>
>
>
>
>
>
>
>
>
>
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> ------------------------------
>
> Message: 2
> Date: Mon, 23 Nov 2009 10:10:22 +0000
> From: Fred Manby <fred.manby at bristol.ac.uk>
> Subject: Re: [molpro-user] wrong PBE0 energies
> To: molpro-user at molpro.net
> Message-ID: <B8EE3409-7FB1-407A-ADFC-3093629F6B6F at bris.ac.uk>
> Content-Type: text/plain; charset="utf-8"
>
> Dear Wenli
>
> Many thanks for alerting us to this discrepancy. I have reproduced the
> problem (using yet another code, Turbomole) and will fix the problem.
>
> Best wishes
>
> Fred
>
> On 13 Nov 2009, at 17:30, Zork Zou wrote:
>
> > Dear all,
> >
> > I performed some DFT calculations, and found that the PBE0 energies
> > are different from the results of other programs (Gaussian, Gamess,
> > Dalton, ?). For example,
> >
> > Ne atom: STO-3G
> > -126.88397 (Molpro)
> > -126.85545 (other)
> >
> > He atom: 6-31G
> > -2.89155 (Molpro)
> > -2.88769 (other)
> >
> > I also checked the BLYP and B3LYP functionals. The energies agree
> > very well. So there must be something different in Molpro?s PBE0
> > from the other programs.
> >
> > Wenli
> >
> >
> > ?????????????????
> > _______________________________________________
> > Molpro-user mailing list
> > Molpro-user at molpro.net
> > http://www.molpro.net/mailman/listinfo/molpro-user
>
> --
> Dr Fred Manby
> Centre for Computational Chemistry
> School of Chemistry, University of Bristol
> Bristol BS8 1TS, UK
> +44 117 92 (87664)
> http://www.chm.bris.ac.uk/pt/manby/
>
> Computational Molecular Science 2010: http://www.chm.bris.ac.uk/cms
>
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> End of Molpro-user Digest, Vol 16, Issue 19
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>



-- 
Jayashree
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