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

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 → 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 → ClO + O₂. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 422–430, 2007 [ABSTRACT FROM AUTHOR]