<b>Ozone Ultraviolet Photolysis. IV.</b> O2† + O(3P) <b>Vibrational Energy Transfer</b>

Abstract

The rate of relaxation of vibrationally excited O2† in high vibrational levels of the X 3Σg− ground state was measured following flash photolysis of O3−Ar mixtures. The relaxation rate is proportional to the O(3P) concentration when the [O(3P)]/[O3] ratio is not small. The data are analyzed assuming that the constants conform to the systematic relationship, kij = k10[1+β(i−1)] exp[−γ(i−j−1)], where i is the initial state and j is the final state with i&amp;gt;j. β determines the dependence on energy level and γ the dependence on multiple quantum transitions. Using k10 = 6 × 108 liter/mole·sec from Kiefer and Lutz, the values β=0.04 and γ=0 best represent the data. That is, the large increase in relaxation rate with energy level is best explained by multiple quantum transitions. With this interpretation the shock-tube studies of Kiefer and Lutz, the trajectory calculations by Brieg, and the results of this study are self-consistent.