Inclusion of non-orthogonality on the valence bond charge-transfer model for nonlinear optical properties of push-pull molecules

E. Squitieri, M. Gorayeb, J. L. Paz, Vladimiro Mujica

Research output: Contribution to journalArticle


In models based on valence bond theory for predicting, nonlinear optical properties of push-pull molecules, the wave functions representing resonance structures are assumed to be orthogonal. We have extended the two-state valence bond charge-transfer model to include non-zero overlap integrals. The resulting model leads to analytic formulae for the polarizability and hyperpolarizabilities, which are related to the overlap and other molecular parameters. In particular we report, as a function of the overlap: (i) relatively weak dependence of the first-order polarizability; (ii) significant variations in both the magnitude and the shape of the response curves corresponding to the second- and third-order polarizabilities. This result may be of relevance in the context of optical switching effects induced by chemical changes (related to the overlap) rather than the more conventional field-induced effect.

Original languageEnglish
Pages (from-to)1805-1811
Number of pages7
JournalMolecular Physics
Issue number12
Publication statusPublished - Jun 20 2003


ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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