Abstract

The kinetics and dynamics of several O + O2 isotope exchange reactions have been investigated on a recently determined accurate global O3 potential energy surface using a time-dependent wave packet method. The agreement between calculated and measured rate coefficients is significantly improved over previous work. More importantly, the experimentally observed negative temperature dependence of the rate coefficients is for the first time rigorously reproduced theoretically. This negative temperature dependence can be attributed to the absence in the new potential energy surface of a submerged "reef" structure, which was present in all previous potential energy surfaces. In addition, contributions of rotational excited states of the diatomic reactant further accentuate the negative temperature dependence.

Department(s)

Chemistry

Research Center/Lab(s)

Center for High Performance Computing Research

Keywords and Phrases

Isotopes; Lasers; Masers; Potential energy surfaces; Temperature distribution, Ab initio potential energy surface; Exchange reaction; Isotope exchange reactions; Kinetics and dynamics; Negative temperatures; Rate coefficients; Rotational excited state; Time-dependent wave packet method, Quantum chemistry

International Standard Serial Number (ISSN)

0021-9606

Document Type

Article - Journal

Document Version

Final Version

File Type

text

Language(s)

English

Rights

© 2014 American Institute of Physics (AIP), All rights reserved.

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