[molpro-user] Bad Localized Orbitals?

[Gerald Knizia]

Dear Matthias,
you could try using IboView (www.iboview.org) for visualization. Apart
from making prettier pictures, it also automatically derives reasonable
iso values by determining the iso values in such a away that they
enclose 80% of the electron's density (or any other threshold you set
up).

Regarding the localization: I think the localization defaults to Pipek-
Mezey. If you want interpretable orbitals, it might be better to switch
to IBO, like this:

{df-rhf}
{ibba}  ! intrinsic basis bonding analysis (makes IBO localized
orbitals)

Best wishes,
Gerald

On Fri, 2017-02-10 at 12:45 -0700, Matthias Heger wrote:
> Dear Peter,
> 
> thank you for your reply! After looking through your files and
> seeing 
> the same thing, I finally realized that the problem was actually
> very 
> mundane. The two cube files default to the unfortunate isovalues of 
> about 0.103 and 0.013 in Chimera, and it seems I didn't pay close
> enough 
> attention to spot the difference between those numbers.
> 
> So, everything is ok. No reason to worry.
> 
> Best,
> Matthias
> 
> --
> Dr. Matthias Heger
> Department of Chemistry, University of Alberta
> 11227 Saskatchewan Drive NW
> Edmonton, AB T6G 2G2, Canada
> 
> Office: CCIS 4-151
> Email: heger at ualberta.ca
> 
> Am 10-Feb-2017 um 11:23 AM schrieb Peter Knowles:
> > I can’t reproduce this problem at all. I get solid localised
> > orbitals 3.1 and 4.1, visualising either the cube files with VMD,
> > or (more easily) generating a molden file and using jmol. Please
> > have a look at the files in
> > https://www.odrive.com/s/252b3e9c-8f69-4875-8f2d-063b88e503ed-589e0
> > 2ca
> > 
> > Best regards,
> > Peter Knowles
> > 
> > > On 9 Feb 2017, at 21:26, Matthias Heger <heger at ualberta.ca>
> > > wrote:
> > > 
> > > Hello everyone,
> > > 
> > > I've been doing a quick LMP2 calculation in Molpro 2015.1 on
> > > formaldehyde. My input is fairly straightforward, and attached to
> > > the end of this email. With NPASEL=0.07, the domain definitions
> > > in the output look like this:
> > > 
> > >   Orb.   Atom     Charge      Total
> > >   3.1    2 C       1.11
> > >          4 H       0.88        1.99
> > >   4.1    2 C       1.11
> > >          3 H       0.88        1.99
> > >   5.1    1 O       1.31
> > >          2 C       0.68        2.00
> > >   6.1    1 O       1.36
> > >          2 C       0.64        2.00
> > >   7.1    1 O       1.91        1.91
> > >   8.1    1 O       1.97        1.97
> > > 
> > > When visualizing the localized orbitals, #4.1 looks like I would
> > > expect a localized C-H bond orbital to turn out. However,
> > > something bad seems to be going on with orbital 3.1:
> > > http://i.imgur.com/JJn1Kwl.png
> > > I noticed something similar happening in pentane. The C-H bond
> > > orbitals on one end of the molecule looked fine, while those on
> > > the other end were quite messy.
> > > 
> > > Does anyone know what's going on here? How will this impact my
> > > correlation energies?
> > > 
> > > Best,
> > > Matthias
> > > 
> > > 
> > > ***
> > > basis=vtz
> > > angstrom
> > > geomtyp=xyz
> > > orient,mass
> > > symmetry,nosym
> > > geometry={
> > >    4
> > > fa
> > > O          0.0000000000        0.0000000000        0.6034321216
> > > C          0.0000000000        0.0000000000       -0.6053608971
> > > H          0.0000000000        0.9357726712       -1.1823928760
> > > H          0.0000000000       -0.9357726712       -1.1823928760}
> > > df-hf
> > > {df-lmp2
> > > local,npasel=0.07,savorb=3000.2}
> > > {cube,Formaldehyde_loc
> > > orbital,occ,record=3000.2,type=local}
> > > 
> > > --
> > > Dr. Matthias Heger
> > > Department of Chemistry, University of Alberta
> > > 11227 Saskatchewan Drive NW
> > > Edmonton, AB T6G 2G2, Canada
> > > 
> > > Office: CCIS 4-151
> > > Email: heger at ualberta.ca
> > > _______________________________________________
> > > Molpro-user mailing list
> > > Molpro-user at molpro.net
> > > http://www.molpro.net/mailman/listinfo/molpro-user
> > 
> > --
> > Prof. Peter J. Knowles
> > School of Chemistry, Cardiff University, Main Building, Park Place,
> > Cardiff CF10 3AT, UK
> > Telephone: +44 29 208 79182
> > Email: KnowlesPJ at Cardiff.ac.uk
> > 
> > Yr Athro Peter J. Knowles
> > Yr Ysgol Cemeg, Prifysgol Caerdydd,
> > Prif Adeilad, Plas y Parc
> > Caerdydd CF10 3AT, DU
> > Ffôn: +44 2920 879182
> > Ebost: KnowlesPJ at Caerdydd.ac.uk
> > Ysgrifennwch ataf yn Gymraeg neu Saesneg
> > 
> > 
> > 
> > 
> > 
> > 
> > 
> > 
> 
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