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Unimolecular reaction rate theory for transition states of any looseness. 3. Application to methyl radical recombination

Wardlaw, David M. and Marcus, R. A. (1986) Unimolecular reaction rate theory for transition states of any looseness. 3. Application to methyl radical recombination. Journal of Physical Chemistry, 90 (21). pp. 5383-5393. ISSN 0022-3654 . https://resolver.caltech.edu/CaltechAUTHORS:20150629-124940889

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Abstract

The theory for unimolecular reactions described in part 1 is applied to the recombination of methyl radicals in the high-pressure limit. The model potential energy surface and the methodology are briefly described. Results are presented for the recombination rate constant k_ ∞ at T = 300, 500, 1000, and 2000 K. Canonical and Boltzmann averaged microcanonical values of k_ ∞ are compared, and the influence of a potential energy interpolation parameter and a separation-dependent symmetry correction on k_ ∞ are examined. Earlier theoretical models and extensive experimental results are compared with the present results which are found to have a negative temperature dependence. The present results agree well with some of the available but presently incomplete experimental determinations of the high-pressure recombination rate constant for this reaction over the 300-2000 K temperature range. There is also agreement with a decomposition rate constant for a vibrationally excited ethane molecule produced by chemical activation.


Item Type:Article
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http://dx.doi.org/10.1021/j100412a098DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100412a098PublisherArticle
Additional Information:© 1986 American Chemical Society. Received March 25, 1986. It is a pleasure to acknowledge the support of this research by the National Science Foundation (R.A.M.) and by the Natural Sciences and Engineering Research Council of Canada (D.M.W.).
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NSFUNSPECIFIED
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics7395
Issue or Number:21
Record Number:CaltechAUTHORS:20150629-124940889
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150629-124940889
Official Citation:Wardlaw, D. M., & Marcus, R. A. (1986). Unimolecular reaction rate theory for transition states of any looseness. 3. Application to methyl radical recombination. The Journal of Physical Chemistry, 90(21), 5383-5393. doi: 10.1021/j100412a098
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58674
Collection:CaltechAUTHORS
Deposited By: Joanne McCole
Deposited On:29 Jun 2015 21:30
Last Modified:03 Oct 2019 08:38

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