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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
  • Yaqin Li
  • Zhigang Sun
  • Bin Jiang
  • Daiqian Xie
  • Richard Dawes, Missouri University of Science and Technology
  • Hua Guo
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
Document Type
Article - Journal
Document Version
Final Version
File Type
text
Language(s)
English
Rights
© 2014 American Institute of Physics (AIP), All rights reserved.
Publication Date
8-1-2014
Citation Information
Yaqin Li, Zhigang Sun, Bin Jiang, Daiqian Xie, 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 Iss. 8 (2014) ISSN: 0021-9606
Available at: http://works.bepress.com/richard_dawes/52/