Mode Selectivity for a "Central" Barrier Reaction: Eight-Dimensional Quantum Studies of the O((3)P) + CH4 → OH + CH3 Reaction on an Ab Initio Potential Energy Surface.
The dynamics of a combustion reaction, namely, O((3)P) + CH4 → OH + CH3, is investigated with an eight-dimensional quantum model that includes representatives of all vibrational modes of CH4 and with a full-dimensional quasi-classical trajectory (QCT) method. The calculated excitation functions for the ground vibrational state CH4 agree well with experiment. Both quantum and QCT results suggest that excitation of the stretching modes of CH4 enhances the reaction, while the bending and umbrella modes have a smaller impact on reactivity, again consistent with experimental findings. However, none of the vibrational excitations has comparable efficiency in promoting the reaction as translational energy.
†Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Centre for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China.
Rui
R
Liu
†Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Centre for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China.
Minghui
M
Yang
‡Laboratory of Molecular Structure and Dynamics, Institute of Chemistry, Eötvös University, H-1518, Budapest 112, P.O. Box 32, Hungary.
Gábor
G
Czakó
§Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Joel M
JM
Bowman
⊥Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Jun
J
Li
⊥Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Hua
H
Guo
combustion; methane; mode-specific reactivity; quantum scattering; reaction dynamics