[molpro-user] polari and quadrupole-quadrupole polarizabilities

[Glen Jenness]

Cong,
We had a feeling that might have been the case.

Thanks!
Glen


> Dear Glen,
>
>  It seems the polarizability calculated in MOLPRO is
> - <<A;B>> =   \sum_n  ( <0 | A |n > <n | B | 0 > +  <0 | B |n > <n | A
> | 0 > ) / (E_n - E_0)
>
>   The << .. >> notation follows J. Olsen and P. Jørgensen, JCP, 82, 3235
>
>  While the common used Cartesian, quadrupole-quadrupole polarizability
> adopted the Buckingham convention, Adv. Chem. Phys. 12, 107-143,
> (1967) or Stone, the theory of intermolecular forces, P21
>
> C_{abcd} =  1/3 \sum_n  ( <0 | Q_ab |n > <n | Q_cd | 0 > +  <0 | Q_cd
> |n > <n | Q_ab | 0 > ) / (E_n - E_0)
>
> That takes the factor of 1/3
>
> best regards
> Cong Wang
>
> Ph. D. Student
> Department of Chemistry
> Laboratory for Instruction in Swedish
> University of Helsinki
> A.I. Virtanens plats 1
> P.O. Box 55
> FI-00014 University of Helsinki
> FINLAND
>
>
>
> On Fri, May 28, 2010 at 4:37 PM, Glen Jenness <grj3 at pitt.edu> 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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