Communication: Highly accurate ozone formation potential and implications for kinetics

Abstract

Atmospheric ozone is formed by the O + O(2) exchange reaction followed by collisional stabilization of the O(3)(∗) intermediate. The dynamics of the O + O(2) reaction and to a lesser extent the O(3) stabilization depend sensitively on the underlying potential energy surface, particularly in the asymptotic region. Highly accurate Davidson corrected multi-state multi-reference configuration interaction calculations reported here reveal that the minimal energy path for the formation of O(3) from O + O(2) is a monotonically decaying function of the atom-diatom distance and contains no "reef" feature found in previous ab initio calculations. The absence of a submerged barrier leads to an exchange rate constant with the correct temperature dependence and is in better agreement with experiment, as shown by quantum scattering calculations.