[molpro-user] polari and quadrupole-quadrupole polarizabilities

[Peter Knowles]

I don't see the discrepancy at all. In table 4 of Dehez et al you will find 23.602 for (an approximation to) the MP2 zz,zz polarizability, which is close to the 23.692 that you get from

bohr
geometry={o,,,.222275;h,1.42931,,-.889101;h,-1.42931,,-.889101;}
cartesian
basis,6-311++G(2d,2p)
rhf;
{mp2;core;polari,dm,qm}

Smaller basis sets can, of course, give smaller polarizabilities.

What am I missing?
Peter

On 28 May 2010, at 14:37, Glen Jenness wrote:

> Dear Molpro users,
> I recently used the polari keyword for both HF and MP2 to calculate
> quadrupole-quadrupole polarizabilities.  I opted to use water as a simple
> system with aug-cc-pVDZ basis set.
> 
> However, I noticed some inconsistencies with the values from MOLPRO2009
> and other methods/literature values.  If we consider the Czz,zz term we
> get (in a.u.):
> 
> MOLPRO:  24.13
> Bishop Method:  7.79
> Dehez et al.:  7.87
> 
> For some references:
> Bishop method is outlined in Theor Chim Acta, 71, 247-253 (1987)
> Dehez et al. is literature value from J. Phys. Chem. A, 104, 1293-1303 (2000)
> 
> It's clear that the MOLPRO values are off by about a factor of 3.
> 
> Glen Jenness
> 
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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 74805 Email KnowlesPJ at Cardiff.ac.uk 
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