[molpro-user] Li+ MP2 problem

Tim Wright Tim.Wright at nottingham.ac.uk
Sat Jan 2 14:49:59 GMT 2010

I think this is because you are implicitly using the frozen core
approximation in the MP2 procedure.  For Li this would keep the two 1s
electrons frozen, so only the single 2s electron would be active; for
Li+, there are therefore no active electrons.  You will need to
explicitly include the 1s electrons if you wish to correlate them.  The
same would happen for CCSD etc.

Similar problems would arise for other alkali metal cations.



-----Original Message-----
From: molpro-user-bounces at molpro.net
[mailto:molpro-user-bounces at molpro.net] On Behalf Of AYORINDE HASSAN
Sent: 01 January 2010 09:13
To: molpro-user at molpro.net
Subject: [molpro-user] Li+ MP2 problem

Hi all,
I am a new molpro user. I was trying to run an mp2 energy calculation of
Li cation(Li+) as a test, but I always encounter an error which is
absent when i run hartree fock or dft. The error is as follows:
 GLOBAL ERROR fehler on processor   2

 GLOBAL ERROR fehler on processor   0

1PROGRAM * MP2 (Closed-shell)     Authors: C. Hampel, H.-J. Werner,
1991, M. Deegan, P.J. Knowles, 1992,  U. Schumann, 2001

 The number of valence orbitals is .le. 0.
 One possible cause of this is that there are no orbitals available, ie
you might have forgotten
 to do a Hartree-Fock calculation. Another possiblity is that the number
of electrons is .le. half
 the number of uncorrelated core orbitals.

The inout file is as follows:
Geometry specification:
Li,	0.,	0.,	0.
! LITHIUM       (10s,6p,4d) -> [5s,3p,2d]
! LITHIUM       (10s,6p,4d) -> [5s,3p,2d]
s, LI , 1359.4466000, 204.0264700, 46.5495410, 13.2325940, 4.2861480,
1.4955420, 0.5422380, 0.0739680, 0.0280950, 0.0106710
c, 1.5, 0.0008440, 0.0064860, 0.0324770, 0.1174200, 0.2945800
c, 6.7, 0.4495150, 0.5422380
c, 8.8, 1.0000000
c, 9.9, 1.0000000
c, 10.10, 1.0000000
p, LI , 4.1700000, 1.1725600, 0.3292700, 0.0927100, 0.0260700, 0.0073310
c, 1.4, 0.0051120, 0.0209070, 0.0916720, 0.4492600
c, 5.5, 1.0000000
c, 6.6, 1.0000000
d, LI , 0.3292700, 0.0927100, 0.0260700, 0.0073310
c, 1.2, 0.1597570, 1.4754840
c, 3.4, 0.3705780, 0.0178470

Can someone kindly tell me why I am encountering this error at the MP2
level? I am missing something in my input file?

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