Published in

American Institute of Physics, The Journal of Chemical Physics, 20(122), p. 204108, 2005

DOI: 10.1063/1.1909031

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Variational calculation of vibrational linear and nonlinear optical properties

Journal article published in 2005 by Miquel Torrent Sucarrat ORCID, Josep Maria Luis Luis ORCID, Bernard Kirtman
This paper is available in a repository.
This paper is available in a repository.

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Abstract

A variational approach for reliably calculating vibrational linear and nonlinear optical properties of molecules with large electrical and/or mechanical anharmonicity is introduced. This approach utilizes a self-consistent solution of the vibrational Schrodinger equation for the complete field-dependent potential-energy surface and, then, adds higher-level vibrational correlation corrections as desired. An initial application is made to static properties for three molecules of widely varying anharmonicity using the lowest-level vibrational correlation treatment (i.e., vibrational Møller-Plesset perturbation theory). Our results indicate when the conventional Bishop-Kirtman perturbation method can be expected to break down and when high-level vibrational correlation methods are likely to be required. Future improvements and extensions are discussed.