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Product quantum state distributions in unimolecular reactions involving highly flexible transition states

Marcus, R. A. (1986) Product quantum state distributions in unimolecular reactions involving highly flexible transition states. Journal of Chemical Physics, 85 (9). pp. 5035-5040. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:MARjcp86

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Abstract

An expression for the distribution of quantum states of the reaction products of unimolecular dissociations is obtained, based on statistical theory. A recently formulated RRKM-type treatment of unimolecular reactions with highly flexible transition states is used to obtain a distribution of quantum states of the products, by introducing an adiabatic approximation for motion from transition state to products. Any impulsive (nonadiabatic) exit channel effects are neglected thereby. Both the final yields of the quantum states of the products and the time evolution of these states are considered. The time evolution of the yield of the products can permit a direct test of non-RRKM effects and, additionally via the long-time component, of other aspects of RRKM theory. The long-time component of the yield of individual quantum states of the products then provides a test of the additional (here, adiabatic) approximation. Such tests are the more definitive the narrower the distribution of initial E's and J's of the dissociating molecule.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.451693DOIUNSPECIFIED
http://link.aip.org/link/?JCPSA6/85/5035/1PublisherUNSPECIFIED
Additional Information:© 1986 American Institute of Physics. Received 10 March 1986; accepted 8 July 1986. It is a pleasure to acknowledge the support of this research by the National Science Foundation and helpful discussions with my colleague, Ahmed Zewail. I am also particularly indebted to my collaborator, David Wardlaw, whose critical reading of the manuscript led to significant improvements. Noyes Laboratory of Chemical Physics, Contribution No. 7407.
Funders:
Funding AgencyGrant Number
National Science FoundationUNSPECIFIED
Subject Keywords:DISSOCIATION, ISOMERIZATION, CHEMICAL REACTION KINETICS, STATISTICAL MECHANICS
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Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics7407
Record Number:CaltechAUTHORS:MARjcp86
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:MARjcp86
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11395
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:13 Aug 2008 04:45
Last Modified:26 Dec 2012 10:13

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