[molpro-user] puzzling XeF2 result (corrected)

[Peter Knowles]

This is a ‘feature’ of the low-level basis set interface - it is expecting an atom reference, not a chemical element. So
spdfg, F1, avqz
will set you in the right direction.

It is of course a problem that the program silently condones what you did, and fails to give you a basis set, and we will do what we can to fix that.

Peter

> On 25 Jul 2017, at 13:44, Hoffman, Gerald <GHOFFMAN at edinboro.edu> wrote:
> 
> I made an embarrassing mistake in my previous post, which has been corrected below.  However, I'm still getting the wrong energy:
> 
> Using the input file below, I attempted an SCF calculation on the XeF2 molecule using the Stuttgart ECP and basis set for Xe and the Aug-cc-pVQZ basis set for F.  I obtained a total energy of -58.43 Hartrees.  This is clearly wrong.  Each of the fluorines by itself ought to have an energy of -99. Hartrees, and in previous versions of Molpro, the energy of this molecule is around -214. Hartrees.  The calculation of XeF gives a reasonable value (-115. Hartrees).
> 
> Help would be appreciated.
> 
> Input file:
> 
> ***,XeF2
> memory,50,M
> 
> angstrom
> 
> geometry={
> Xe    0.0000    0.0000    0.0000
> F1    0.0000    0.0000   -1.99
> F2    0.0000    0.0000    1.99
> }
> 
> basis={
> !
> ! Xenon ecp
> !
> ecp,Xe,46,5,3;
> 1;                                                                              ! h
> 2,1.00,0.00
> 2;                                                                              ! s-h
> 2,3.940263,122.76382934;2,2.277264,8.30885115;
> 2;                                                                              ! p-h
> 2,3.028373,68.82300437;2,1.394319,3.64674233;
> 2;                                                                              ! d-h
> 2,2.122605,23.65207854;2,0.798669,3.25844113;
> 2;                                                                              ! f-h
> 2,6.164360,-47.70319876;2,1.542374,-6.54113991;
> 1;                                                                              ! g-h
> 2,1.847892,-7.10585060;
> 2;                                                                              ! so-ecp
> 2,3.028373,-1.74609113*(2/3);2,1.394319,2.19487257*(2/3);
> 2;                                                                              ! so-ecp
> 2,2.122605,-1.04567591*(2/5);2,0.798669,0.27199291*(2/5);
> 1;                                                                              ! so-ecp
> 2,6.164360,0.20772207*(2/7);
> !
> ! Xenon basis
> !
> spdfg,Xe,ecp46mwb_vqz
> s,Xe,0.040702,0.019340;c,1.1,1.00;c,2.2,1.00;
> p,Xe,0.026108,0.012447;c,1.1,1.00;c,2.2,1.00;
> d,Xe,0.089444;c,1.1,1.00;
> f,Xe,0.132301;c,1.1,1.00;
> !
> ! Fluorine-basis
> !
> spdfg,F,avqz
> s,2,0.034376;c,1.1,1.00;
> p,2,0.026272;c,1.1,1.00;
> d,2,0.0828;c,1.1,1.00;
> }
> 
> cpp,init,1;
> Xe,1,0.8345,,,0.97391;
> 
> {rhf;wf,26,1,0;}
>  
> 
> 
> Gerry Hoffman
> 
> Gerald J. Hoffman, Ph. D.
> 
> Associate Professor of Chemistry
> 
> Edinboro University of Pennsylvania
> 
> 230 Scotland Road
> 
> Edinboro, PA 16444
> 
>  
> 814-732-2813
> 
>  
> ghoffman at edinboro.edu
> 
>  
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--
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
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