Communication: Highly Accurate Ozone Formation Potential and Implications for Kinetics
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.
R. Dawes et al., "Communication: Highly Accurate Ozone Formation Potential and Implications for Kinetics," Journal of Chemical Physics, vol. 135, no. 8, American Institute of Physics (AIP), Aug 2011.
The definitive version is available at http://dx.doi.org/10.1063/1.3632055
Keywords and Phrases
Ab initio calculations; Atmospheric ozone; Collisional stabilization; Davidson; Exchange rates; Exchange reaction; Minimal energy; Multi state; Multireference configuration; Ozone formation; Quantum scattering; Temperature dependence, Atmospheric chemistry; Calculations; Ozone; Quantum chemistry; Rate constants; Stabilization, Reaction kinetics
International Standard Serial Number (ISSN)
Article - Journal
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