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Intramolecular dynamics. I. Curvilinear normal modes, local modes, molecular anharmonic Hamiltonian, and application to benzene

Zhang, Yongfeng and Klippenstein, Stephen J. and Marcus, R. A. (1991) Intramolecular dynamics. I. Curvilinear normal modes, local modes, molecular anharmonic Hamiltonian, and application to benzene. Journal of Chemical Physics, 94 (11). pp. 7319-7334. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:ZHAjcp91

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Abstract

The Hamiltonian based on curvilinear normal modes and local modes (CNLM) is discussed using Wilson's exact vibrational Hamiltonian as basis, the CNLM representation diagonalizing only the normal mode block of FG matrix in curvilinear internal coordinates. Using CNLM the kinetic and potential energy operators for benzene are given, including cubic and quartic anharmonicity in the potential energy and cubic and quartic terms in the kinetic energy expansion in curvilinear coordinates. Using symmetrized coordinates and cubic and higher force constants the number and identity of the independent symmetry allowed (A1g) such force constants are obtained. The relation to conventional anharmonic force constants is then given and the allowed contributions of the latter are obtained. The results are applied to CH overtone spectra and intramolecular vibrational dynamics in Part III of this series.


Item Type:Article
Additional Information:©1991 The American Physical Society. Received 3 December 1990; accepted 5 February 1991. This research was supported by the Caltech Consortium in Chemistry and Chemical Engineering; Founding Members: E. I. du Pont de Nemours and Company, Inc., Eastman Kodak Company, and Minnesota Mining and Manufacturing Company. It is a pleasure to acknowledge also the support of this research by a grant from the National Science Foundation.
Record Number:CaltechAUTHORS:ZHAjcp91
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:ZHAjcp91
Alternative URL:http://dx.doi.org/10.1063/1.460216
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7078
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:08 Jan 2007
Last Modified:26 Dec 2012 09:28

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