[molpro-user] puzzling XeF2 result

[Klaus Doll]

Dear Gerald,
I think you have to  change the basis input for F to:

spdfg,F,avqz
s,F,0.034376;c,1.1,1.00;
p,F,0.026272;c,1.1,1.00;
d,F,0.0828;c,1.1,1.00;

and in the wf-card, the number of electrons should be 26.

For me, the input below gives an energy of -214.22... Hartrees:

***,XeF2

memory,50,M
gprint,basis

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,F,0.034376;c,1.1,1.00;
p,F,0.026272;c,1.1,1.00;
d,F,0.0828;c,1.1,1.00;
}


cpp,init,1;
Xe,1,0.8345,,,0.97391;


{rhf;wf,26,1,0;}

pop;









On 07/24/2017 09:57 PM, Hoffman, Gerald wrote:
> 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={
>
> Xe0.00000.00000.0000
>
> F10.00000.0000 -1.99
>
> F20.00000.00001.99
>
> }
>
>
> 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>
>
>
>
> _______________________________________________
> Molpro-user mailing list
> Molpro-user at molpro.net
> http://www.molpro.net/mailman/listinfo/molpro-user

Klaus Doll
University of Stuttgart
Molpro Quantum Chemistry Software
Institute of Theoretical Chemistry
Pfaffenwaldring 55
D-70569 Stuttgart
Germany
e-mail: doll at theochem.uni-stuttgart.de

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