Mechanism of Singlet Molecular Oxygen Formation from Photolysis of Ozone at 2537 Å

Abstract

Emission from ${\mathrm{O}}_2{(}^1{\Delta }_g)$ and ${\mathrm{O}}_2{(}^1{\Sigma }_g)$ is observed from photolysis of ozone–oxygen mixtures at 2537 Å. The ${\mathrm{O}}_2{(}^1{\Sigma }_g)$ is formed by energy transfer from $\mathrm{O}{(}^1\mathrm{D)}$ and the relative rates of removal of $\mathrm{O}{(}^1\mathrm{D)}$ by O₂, N₂, and O₃ are found to be 1:0.7:9.7, respectively. The ${\mathrm{O}}_2{(}^1{\Delta }_g)$ is formed directly by photolysis. Photolysis and the reaction of $\mathrm{O}{(}^3\mathrm{P)}$ and $\mathrm{O}{(}^1\mathrm{D)}$ with O₃ are discussed as sources of both O₂ singlet states.