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Rotational–Translational Energy Transfer. II. Comparison of Action-Angle Solution in the Near-Static Approximation with Exact Results

Cohen, Audrey O. and Marcus, R. A. (1970) Rotational–Translational Energy Transfer. II. Comparison of Action-Angle Solution in the Near-Static Approximation with Exact Results. Journal of Chemical Physics, 52 (6). pp. 3140-3151. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:COHjcp70

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Abstract

In Part I, the differential equations for molecular rotational–vibrational–translational energy transfer were re-expressed in terms of action-angle variables. In the present paper, approximate integral solutions and exact results for rotational–translational transfer are compared for a wide range of collisional and molecular parameters at small fractional changes in translational energy. The results are in good agreement over the range investigated except at low moments of inertia. Thereby, conditions where the present approximation is best correspond to some which are least accessible by approximate or numerical quantum mechanical methods. The present approximation employs for zeroth order a classical analog of the static approximation in quantum mechanics, rather than the adiabatic approximation, and the results have implications for the ranges of molecular parameters where each should be preferable in the quantum case.


Item Type:Article
Additional Information:©1970 American Institute of Physics. Received 26 September 1969. Acknowledgment is made to the National Science Foundation and to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for their support of this research.
Record Number:CaltechAUTHORS:COHjcp70
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:COHjcp70
Alternative URL:http://dx.doi.org/10.1063/1.1673450
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10711
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:04 Jun 2008
Last Modified:26 Dec 2012 10:04

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