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Classical dynamics of triatomic systems: Energized harmonic molecules

Parr, C. A. and Kuppermann, A. and Porter, R. N. (1977) Classical dynamics of triatomic systems: Energized harmonic molecules. Journal of Chemical Physics, 66 (7). pp. 2914-2931. ISSN 0021-9606.

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The dynamical assumptions underlying the Slater and RRK classical-mechanical theories of unimolecular reaction rates are investigated. The predictions of these theories for several nonlinear, triatomic, harmonically bonded molecular models are compared with the results obtained from the integration of the classical equations of motion. The accuracy of the small-vibration and weak-coupling assumptions are found to break down at energies above about one-quarter of a bond dissociation energy. Nonetheless, the small-vibration approximation predicts reaction frequencies in good agreement with the exact results for the models. The effects of rotation on intramolecular energy exchange are examined and found to be significant.

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Additional Information:Copyright © 1977 American Institute of Physics. Received 26 March 1976. Supported in part by the Energy Research and Development Administration Report Code No. CALT-767P4-49. This work was begun while the authors were associated with the Department of Chemistry, University of Illinois, Urbana IL. Work performed [by C.A.P.] in partial fulfillment of the requirements for the Ph.D. in Chemistry at the California Institute of Technology. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 5290.
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Energy Research and Development AdministrationCALT-767P4-49
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Arthur Amos Noyes Laboratory of Chemical Physics5290
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Deposited On:25 Oct 2008 03:42
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