Vibrational excitation of ozone formed by recombination

Abstract

A new facility coupling flash photolysis and time resolved ir detection and uv absorption diagnostics is described. Its application to studying the reaction $\mathrm{O}+{\mathrm{O}}_2+\mathrm{M}\to {\displaystyle {lim}^{\text{(1)}}}\hspace{0.17em}{\mathrm{O}}_3^{†}+\mathrm{M}$ followed by ${\mathrm{O}}_3^{†}+\mathrm{M}\to {\displaystyle {lim}^{\text{(2)}}}{\mathrm{O}}_3+\mathrm{M}$ with M=O₂ or N₂ and where O₃^† denotes vibrationally excited ozone is described. Our results give k₁=3×10⁻³⁴ cm⁶ sec⁻¹, k₂=2×10⁻¹⁴ cm³ sec⁻¹, φ(ν₁)+φ(ν₃)=1.6, and φ(ν₂)=3.7, where φ(ν_i) is the average number of quanta of energy ν_i, resulting in mode ν_i from each recombination (ν_1,2,3=1103, 701, 1042 cm⁻¹). This partitioning of the product energy accounts for 50% of the 25 kcal exothermicity of the recombination. These results are peculiar to the model used for interpretation, which is discussed in some detail in the text.