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On the relationship of normal modes to local modes in molecular vibrations

Mills, I. and Robiette, A. G. (1985) On the relationship of normal modes to local modes in molecular vibrations. Journal of Molecular Physics, 56 (4). pp. 743-765. ISSN 0026-8976

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To link to this article DOI: 10.1080/00268978500102691

Abstract/Summary

A simple model for the effective vibrational hamiltonian of the XH stretching vibrations in H2O, NH3 and CH4 is considered, based on a morse potential function for the bond stretches plus potential and kinetic energy coupling between pairs of bond oscillators. It is shown that this model can be set up as a matrix in local mode basis functions, or as a matrix in normal mode basis functions, leading to identical results. The energy levels obtained exhibit normal mode patterns at low vibrational excitation, and local mode patterns at high excitation. When the hamiltonian is set up in the normal mode basis it is shown that Darling-Dennison resonances must be included, and simple relations are found to exist between the xrs, gtt, and Krrss anharmonic constants (where the Darling-Dennison coefficients are denoted K) due to their contributions from morse anharmonicity in the bond stretches. The importance of the Darling-Dennison resonances is stressed. The relationship of the two alternative representations of this local mode/normal mode model are investigated, and the potential uses and limitations of the model are discussed.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:7327
Publisher:Taylor and Francis

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