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.

Department(s)

Chemistry

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)

0021-9606

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2011 American Institute of Physics (AIP), All rights reserved.

Publication Date

01 Aug 2011

Link to Full Text

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