Communication: Highly accurate ozone formation potential and implications for kinetics

Abstract

Atmospheric ozone is formed by the O + O2 exchange reaction followed by collisional stabilization of the O3* intermediate. The dynamics of the O + O2 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 + O2 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. © 2011 American Institute of Physics.