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On the theory of the state distribution of the reaction products and rates of unimolecular dissociations

Marcus, R. A. (1988) On the theory of the state distribution of the reaction products and rates of unimolecular dissociations. Chemical Physics Letters, 144 (2). pp. 208-214. ISSN 0009-2614. http://resolver.caltech.edu/CaltechAUTHORS:20150617-104047821

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Abstract

A recent variational implementation of RRKM theory, plus an additional dynamical assumption, is used to calculate the distribution of quantum states of reaction products of unimolecular dissociations. It is assumed that the “conserved” modes of the molecule are vibrationally adiabatic after passage through the transition state region, but that the “transitional modes” are non-adiabatic until the “loose transition state” region is reached. The rate constants k_(EJ) themselves are those of RRKM theory, but, for energies below those needed to yield vibrationally excited products, the phase space theory expression (PST) is obtained for the distribution of rotational states of the products. The product state distribution differs from that of PST when the energy is sufficient to permit product vibrational excitation. The unimolecular reactions considered are those for which there is no potential energy barrier for the reverse reaction (recombination).


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http://dx.doi.org/10.1016/0009-2614(88)87119-7 DOIArticle
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Additional Information:© 1988 Published by Elsevier B.V. Received 23 October 1987; in final form 4 January 1988. It is a pleasure to acknowledge the support of this research by the National Science Foundation. The present paper was prompted by participation in a symposium at Grainau, organized by Ed Schlag and Martin Quack, and I am indebted to them for having arranged such an interesting conference. I should also like to thank Steve Klippenstein for his perceptive comments. This is contribution No. 7684 from the Department of Chemistry at Caltech.
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Caltech Noyes Laboratory of Chemical Physics7684
Record Number:CaltechAUTHORS:20150617-104047821
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150617-104047821
Official Citation:R.A. Marcus, On the theory of the state distribution of the reaction products and rates of unimolecular dissociations, Chemical Physics Letters, Volume 144, Issue 2, 19 February 1988, Pages 208-214, ISSN 0009-2614, http://dx.doi.org/10.1016/0009-2614(88)87119-7. (http://www.sciencedirect.com/science/article/pii/0009261488871197)
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ID Code:58317
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:17 Jun 2015 18:47
Last Modified:17 Jun 2015 18:47

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