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.
Y. Li et al., "Communication: Rigorous Quantum Dynamics of O + O2 Exchange Reactions on an Ab Initio Potential Energy Surface Substantiate the Negative Temperature Dependence of Rate Coefficients," Journal of Chemical Physics, vol. 141, no. 8, American Institute of Physics (AIP), Aug 2014.
The definitive version is available at https://doi.org/10.1063/1.4894069
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)
Article - Journal
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