[molpro-user] Open core hole not working in Molpro 2012.1

[Gerald Knizia]

Dear Henry,
the ordering of orbitals has, for technical reasons, be changed such
that active orbitals *always* follow closed-shell orbitals. This is,
however, only a numbering issue: The higher orbitals can still be higher
in energy. For example, the following two inputs works for me for
computing the Ar p core hole:

-- nr 1: with symmetry:
geometry ={Ar}

basis = 6-311G
{rhf}
{rhf,nitord=1;
   wf,spin=1,charge=1,sym=5;
   rotate,1.5,2.5;
}

-- nr 2: (this also works without symmetry)

nosym;
geometry ={Ar}

basis = 6-311G
{rhf}
{rhf,nitord=1;
   wf,spin=1,charge=1;
   rotate,3.1,9.1;
}

The trick here is that the orbital occupation is frozen at the rotated
input orbitals (nitord=1), without ever re-occupying the orbitals
according to the aufbau principle.

An extended comment on how this (and more complex cases) can be used can
be found in the Molpro manual:
https://www.molpro.net/info/2015.1/doc/manual/node177.html
(under The SCF program/ Advanced use: Core-excited states).

On an unrelated note: the def2-SVP/def2-TZVPP/def2-QZVPP basis sets
(e.g., basis=TZVPP) would do a better job as basis sets for Hartree-Fock
and DFT, and for core hole you probably also want uncontracted basis
sets, and possibly even uncontracted core-correlation basis sets.

Best wishes,
Gerald


On Fri, 2015-12-11 at 12:18 +0000, Banks, Henry wrote:
> Hi,
> 
> I wrote the following input for Argon with a core hole for Molpro 2010.1. It gave an occupation of 1 in the 1.5 orbital and an occupation of 2 in the 2.5 orbital
> 
> ***,Ar22526
> print basis,orbitals
> 
> geometry ={Ar}
> 
> basis = 6-311G
> {hf,
> wf, nelec=17, symmetry=5, spin=1
> occ, 3,2,2,0,2
> open, 1.5
> }
> 
> put,molden,22526.molden;
> 
> —
> 
> However, in the new version of Molpro, the same input file gives an occupation of 2 in the 1.5 orbital and an occupation of 1 in the 2.5 orbital. The hole has been moved.
> 
> Is there a reason why this was changed and is there a work around?
> 
> Thanks,
> 
> Henry
> 
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