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

Abstract

The ClO3 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 rarr ClO + O2 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 + O2 formation are identified: (i) direct abstraction of a terminal oxygen atom from the OClO reactant and (ii) formation of an intermediate ClO3 complex followed by dissociation. The novel potential energy surface gives also a good description of the kinetics of the reaction Cl + O3 rarr ClO + O2. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 422-430, 2007