Ab initio study of vibrational resonacnces in polyatomic molecutles.

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1990

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Ohio State University

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Abstract

An ab initio method for the study of vibrational resonances in polyatomic molecules is presented. It is based on a variational resolution of the vibrational motion within an electronic potential fitted from a grid of ab initio calculated points. An original multiconfigurational self-consistent filed approach (VMCSCF) has been developed in order to elimate the problem of basis set dependecy occuring with usual methods, like configuration interaction (VSCF-CI), when strong vibrational resonances exist. The method is expected to provide configuration mixing coefficientes directly useful to the interpretation of energy and intensity redistribution in spectra. Preliminary results on $H_{2}O, CH_{2}O$ and $C_{2}H_{2}$ are discussed.

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Author Institution: Laboratoire de Chimie Physique Mol\'{e}culaire, CP.160, Universit\'{e} Libre de Bruxelles

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