Ozone Ultraviolet Photolysis. V. Energy Distribution in the O(1D)+O3 Reaction

Abstract

The experiments described in this paper concern the distribution of vibrationally excited O₂^† following flash photolysis of ozone under conditions which permit an improved extrapolation to find the distribution in which they are initially formed. The observed states $\text{v″=14–21}$ are found to have an initial distribution which can reasonably be described by a vibrational temperature, $T_{\mathrm{vib}}\text{=23\hspace{0.17em}400± 1260°}\mathrm{K}$ . The origin of the distribution and the proportionation of product between 2O₂^† and $2\mathrm{O}{(}^3\mathrm{P)+}{\mathrm{O}}_2$ is discussed in terms of a statistical model. This interpretation accounts for the observed distribution of ${\mathrm{O}}_2^i\text{(i=14–21)}$ , it accounts for the predominance of $2\mathrm{O}{(}^3\mathrm{P)+}{\mathrm{O}}_2$ product in gas phase photolysis, and for the predominance of 2O₂ products in photolysis of liquid Ar solutions. An inert gas pressure dependence of the reaction product distribution is predicted and observed qualitatively.