[molpro-user] polari and quadrupole-quadrupole polarizabilities

[Glen Jenness]

There's a factor of 1/3 when converting from spherical to cartesian.



> 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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>
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> Prof. Peter J. Knowles
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