A refined evaluation of the gas-phase dimerization thermodynamics of the ClO radical

Abstract

The title reaction was treated as a convolution of three partial dimerizations, viz., formation of ClOOCl, ClClO2, or ClOClO isomer. Energetics of the dimerizations are derived from a fit to available data in combination with recent quantum-chemical calculations. The thermodynamics of the processes is evaluated with the help of partition functions with the calculated molecular parameters, while due respect has been paid to the dimer isomerism. The isomerism can be particularly significant in evaluating the heat-capacity term, increasing it by more than 10% at some temperatures. The most reliable values of the standard thermodynamic dimerization terms are selected for further applications, especially for elucidating ozone-depletion mechanisms. © 1992 Plenum Publishing Corporation.