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Classical trajectory study of internal energy distributions in unimolecular processes

McDonald, J. D. and Marcus, R. A. (1976) Classical trajectory study of internal energy distributions in unimolecular processes. Journal of Chemical Physics, 65 (6). pp. 2180-2192. ISSN 0021-9606. doi:10.1063/1.433374.

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The method of classical trajectories has been used to study the flow of energy in a molecular system (similar to the molecules CD3Cl and CD3H) representing a chemical activation experiment. Energy distributions are obtained both before and after the breakup of the activated molecule by means of a correlation function technique. Four different potential energy surfaces are employed. It is found that the initial distribution of energy in the activated molecule may or may not be random, depending on the details of the particular surface. This distribution becomes random in less than 5×10−12 sec. The distribution of energy in the final product (CD3) is found to be randomly distributed (as predicted by RRKM theory including angular momentum considerations) for a surface with no exit channel barrier or strong intermode couplings. When these special forces are present nonrandom energy distributions result. Product channel barriers result in an excess of translational energy and exit channel intermode couplings result in nonrandom vibrational distributions. Angular momentum considerations are found to be important in matching the predictions of RRKM theory with the calculations.

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Marcus, R. A.0000-0001-6547-1469
Additional Information:Copyright © 1976 American Institute of Physics. Received 15 March 1976. This work was supported by the National Science Foundation (Grant No. NPS 74-23140) and the National Aeronautics and Space Administration (Grant No. NGR 14-005-202). We wish to thank Professor Bob Ray for the use of his access to the Illiac IV computer, and also to thank Dr. Don Noid for many helpful discussions especially concerning the relation of this work to classical ergodic theory.
Funding AgencyGrant Number
National Science FoundationNPS 74-23140
NASANGR 14-005-202
Issue or Number:6
Record Number:CaltechAUTHORS:MCDjcp76
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ID Code:12681
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Deposited On:19 Dec 2008 06:40
Last Modified:08 Nov 2021 22:32

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