Evidence for lambda doublet propensity in the UV photodissociation of ozone

The photodissociation of O₃ at 266 nm has been studied using velocity mapped ion imaging. We report temperature-dependent vector correlations for the O₂(a¹Δ_g, v = 0, j = 18-20) fragments at molecular beam temperatures of 70 K, 115 K, and 170 K. Both the fragment spatial anisotropy and the v-j correlations are found to be increasingly depolarized with increasing beam temperature. At all temperatures, the v-j correlations for the j = 19 state were shown to be reduced compared to those of j = 18 and 20, while no such odd/even rotational state difference was observed for the spatial anisotropy, consistent with previous measurements. We find that temperature-dependent differences in the populations and v-j correlations between the odd and even rotational states can be explained by a Λ-doublet propensity model. Although symmetry conservation should lead to formation of only the A' Λ-doublet component, and only even rotational states, out-of-plane rotation of the parent molecule breaks the planar symmetry and permits the formation of the A″ Λ-doublet component and odd rotational states. A simple classical model to treat the effect of parent rotation on the v-j correlation and the odd/even rotational population alternation reproduces both the current measurements and previously reported rotational distributions, suggesting that the "odd" behavior originates from a Λ-doublet propensity, and not from a mass independent curve crossing effect, as previously proposed.