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Kinetics and dynamics of O + OClO reaction in a modified many-body expansion potential energy surface for ClO3

✍ Scribed by O. B. M. Teixeira; J. M. C. Marques; A. J. C. Varandas


Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
719 KB
Volume
39
Category
Article
ISSN
0538-8066

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✦ Synopsis


Abstract

The ClO~3~ many‐body expansion potential energy surface of Farantos and Murrell (Int J Quantum Chem 1978, 14, 659) has been modified along the minimum energy path for the reaction O + OClO → ClO + O~2~ such as to conform with the available kinetics data. The dynamics of the title reaction is also studied for temperatures of relevance in stratospheric chemistry. Two mechanisms for ClO + O~2~ formation are identified: (i) direct abstraction of a terminal oxygen atom from the OClO reactant and (ii) formation of an intermediate ClO~3~ complex followed by dissociation. The novel potential energy surface gives also a good description of the kinetics of the reaction Cl + O~3~ → ClO + O~2~. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 422–430, 2007