Ring Polymer Molecular Dynamics Calculations of Thermal Rate Constants for the O((3)P) + CH4 → OH + CH3 Reaction: Contributions of Quantum Effects.
The thermal rate constant of the O((3)P) + CH4 → OH + CH3 reaction is investigated with ring polymer molecular dynamics on a full-dimensional potential energy surface. Good agreement with experimental and full-dimensional quantum multiconfiguration time-dependent Hartree results between 300 and 1500 K was obtained. It is shown that quantum effects, for example, tunneling and zero-point energy, can be effectively and efficiently included in this path-integral based approach implemented with classical trajectories. Convergence with respect to the number of beads is rapid, suggesting wide applicability for other reactions involving polyatomic molecules.
†Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Yongle
Y
Li
‡Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Yury V
YV
Suleimanov
§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
‡Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
William H
WH
Green
†Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Hua
H
Guo
combustion; path integral; reaction rates; tunneling; zero-point energy