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Systematic characterization of transition states for radical decompositions

Grela, M. A. and Colussi, A. J. (1987) Systematic characterization of transition states for radical decompositions. International Journal of Chemical Kinetics, 19 (9). pp. 869-879. ISSN 0538-8066. https://resolver.caltech.edu/CaltechAUTHORS:20150731-120515377

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Abstract

A one-parameter analytical potential energy function for β-bonds in free radicals is described, which accounts quantitatively for their observed stretching frequencies and the position and size of the activation barriers for their fission. It is shown that such a function can be used to characterize a priori the corresponding transition states by assuming that the structural and spectroscopic changes taking place along the minimum energy path track the development of pi bonding rather than following a simple exponential dependence on the reaction coordinate. This procedure, tested by comparing predicted A-factors and isotope effects with experimental data for alkyl radicals and ab-initio calculations on C_2H_5, fully encodes the basic features of radical decomposition reactions and provides a simple, realistic, and self-consistent technique for the estimation of their kinetic parameters.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/kin.550190907DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/kin.550190907/abstractPublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1987 John Wiley & Sons. Received December 17, 1986; Accepted April 20, 1987.
Issue or Number:9
Record Number:CaltechAUTHORS:20150731-120515377
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150731-120515377
Official Citation:Grela, M. A. and Colussi, A. J. (1987), Systematic characterization of transition states for radical decompositions. Int. J. Chem. Kinet., 19: 869–879. doi: 10.1002/kin.550190907
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59110
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:06 Aug 2015 23:11
Last Modified:03 Oct 2019 08:43

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