Communication: highly accurate ozone formation potential and implications for kinetics.

Citation data:

The Journal of chemical physics, ISSN: 1089-7690, Vol: 135, Issue: 8, Page: 081102

Publication Year:
2011
Usage 180
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Citations 54
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Repository URL:
http://scholarsmine.mst.edu/chem_facwork/377; https://works.bepress.com/richard_dawes/50
PMID:
21895148
DOI:
10.1063/1.3632055
Author(s):
Dawes, Richard; Lolur, Phalgun; Ma, Jianyi; Guo, Hua
Publisher(s):
AIP Publishing; American Institute of Physics (AIP)
Tags:
Physics and Astronomy; Chemistry; 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; 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; Temperature dependence, Atmospheric chemistry; Stabilization, Reaction kinetics
article description
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.