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On the Theory of Chemical-Reaction Cross Sections. I. A Statistical-Dynamical Model

Marcus, R. A. (1966) On the Theory of Chemical-Reaction Cross Sections. I. A Statistical-Dynamical Model. Journal of Chemical Physics, 45 (7). pp. 2630-2638. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120829-145327891

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Abstract

A statistical‐dynamical model is formulated for total chemical‐reaction cross sections as a function of the relative velocity and the vibrational and the rotational state of the reactants. It is derived for reactions for which activated‐complex configurations can be defined; reactions with or without steric and activation barriers. A quasiequilibrium is postulated between reacting pairs and activated complexes of the same energy and angular momentum. An integral equation is obtained which is solved for the reaction cross section by introduction of a second postulate: The reaction probability is a function of the excess initial energy along the reaction coordinate (in excess of potential energy barrier, centrifugal potential barrier, and vibrational adiabatic requirements). A possible dynamical origin of the postulates is considered in later papers.


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http://dx.doi.org/10.1063/1.1727983DOIUNSPECIFIED
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Additional Information:© 1966 American Institute of Physics. Received 14 March 1966. Supported by a grant from the National Science Foundation at the University of Illinois and by a National Aeronautics and Space Administration Grant NsG-275-62 while the author was a Visiting Professor at the Theoretical Chemistry Institute of the University of Wisconsin. A portion of the present work was done while the author was a Visiting Professor at the Theoretical Chemistry Institute of the University of Wisconsin during the summer of 1965. The author especially enjoyed the hospitality of Professor Hirschfelder, Professor Bernstein, and their colleagues during that stimulating visit.
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Record Number:CaltechAUTHORS:20120829-145327891
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120829-145327891
Official Citation:On the Theory of Chemical-Reaction Cross Sections. I. A Statistical-Dynamical Model R. A. Marcus, J. Chem. Phys. 45, 2630 (1966), DOI:10.1063/1.1727983
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33684
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:29 Aug 2012 23:17
Last Modified:26 Dec 2012 16:04

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