Computational insight into relations between electronic and vibrational polarizabilities within the two-state valence-bond charge-transfer model

In this paper, the relationship between static vibrational and electronic hyperpolarizabilities of a series of push pull molecules within the two-state valence-bond charge-transfer model are reinvestigated computationally at the Moller-Plesset level of theory. Although the level of theory employed here gives significantly different results for electronic and vibrational counterparts than those obtained by Bishop et al. [D. Bishop, B. Champagne, B. Kirtman, J. Chem. Phys. 109 (1998) 9987] at the RHF level, the overall conclusions remain unchanged: The comparison of ab initio computations with the predictions of the VB-CT model gives a little confidence in the latter. (c) 2007 Elsevier B.V. All rights reserved.