[molpro-user] puzzling XeF2 result

[Jacky LIEVIN]

Dear Gerry,

3 points:

1. The number of electrons is 26 and not 16 … but this doesn’t solve your problem: the RHF energy is then of -58 hartrees.

2. For an unknown reason the fluorine basis set spdfg,F,avqz is ignored, what explains the low energy value. Using spdfg,2,avqz gives a reasonable energy of -214 hartrees.

3. default basis sets are used as uncontracted, but maybe it’s what you want? If not add '’;c’’ to the basis set specification:  spdfg,2,avqz;c

All the best

Jacky

_____________________________________
Prof. Jacky Liévin
Service de Chimie Quantique et Photophysique
Université Libre de Bruxelles, CPi 160/09
50 av F.D. Roosevelt
B-1050 Bruxelles
Belgium
_____________________________________
 

> Le 24 juil. 2017 à 21:57, Hoffman, Gerald <GHOFFMAN at edinboro.edu> a écrit :
> 
> 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 -45.33 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,16,1,0;}
> 
> 
> 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 <mailto:ghoffman at edinboro.edu>
>  
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