An ab initio and semiempirical study of the first- and third-order polarizabilities in benzene and thiophene derivatives: Electron correlation effects

C. Adant, J. L. Brédas, M. Dupuis

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The static first- and third-order polarizabilities of several benzene and thiophene derivatives are evaluated at the ab initio level via an efficacious general finite field approach. The impact of electron correlation is explored by calculating the molecular polarizabilities at the Møller-Plesset second-order perturbation (MP2) theory level using an extended basis set. Further, we examine the influence of molecular architecture on the nonlinear optical response, in particular the switch from an arylethenyl type of structure to a quinoid structure. Finally, we apply the correction vector method combined with the intermediate neglect of differential overlap - single and double excitation configuration interaction (INDO-SDCI) technique to evaluate the optical nonlinearities at the semiempirical level. The reliability of this procedure is established by comparison with the corresponding high-level ab initio polarizability values. The results clearly show the sensitive dependence of the nonlinear optical properties on electron correlation effects that are found to quantitatively and qualitatively affect the third-order polarizability values.

Original languageEnglish
Pages (from-to)3025-3031
Number of pages7
JournalJournal of Physical Chemistry A
Issue number16
Publication statusPublished - Apr 17 1997


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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