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Unimolecular reaction rate theory for highly flexible transition states. 2. Conventional coordinate formulas for the various possible fragment combinations: miscellaneous topics

Klippenstein, Stephen J. and Marcus, R. A. (1988) Unimolecular reaction rate theory for highly flexible transition states. 2. Conventional coordinate formulas for the various possible fragment combinations: miscellaneous topics. Journal of Physical Chemistry, 92 (19). pp. 5412-5417. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20150624-084938500

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Abstract

A method for using conventional coordinates in the implementation of RRKM theory for unimolecular dissociations was described in part 1 of this series, for the case where both fragment molecules are nonlinear. The corresponding formalism for all possible types of fragments, atomic, linear, and nonlinear fragments and their combinations, is presented here. Also discussed analytically is the tendency, in a unimolecular dissociation, for the position of the transition state to move to shorter fragment-fragment separation distances with increasing total energy E. This tendency has marked consequences, including increasing deviation of rate constants from those of phase space theory with increasing E and, in the case of fragment-fragment recombination, a corresponding tendency for high-pressure rate constants to decrease with increasing temperature. Two other topics considered in this paper are the case of two minima in the variational calculation and the role of the repulsive potential energy curves in the unimolecular dissociations under consideration.


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http://dx.doi.org/10.1021/j100330a018 DOIArticle
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Additional Information:© 1988 American Chemical Society. Received: January 26, 1988; In Final Form: March 30, 1988. We are pleased to acknowledge the support of this research by a grant from the National Science Foundation.
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics7731
Record Number:CaltechAUTHORS:20150624-084938500
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150624-084938500
Official Citation:Unimolecular reaction rate theory for highly flexible transition states. 2. Conventional coordinate formulas for the various possible fragment combinations: miscellaneous topics Stephen J. Klippenstein and R. A. Marcus The Journal of Physical Chemistry 1988 92 (19), 5412-5417 DOI: 10.1021/j100330a018
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58574
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:24 Jun 2015 16:21
Last Modified:24 Jun 2015 16:21

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