Full dimensional quantum rate coefficients and kinetic isotope effects from ring polymer molecular dynamics for a seven-atom reaction OH + CH[subscript 4] → CH[subscript 3] + H[subscript 2]O
Author(s)
Allen, Joshua W.
Green, William H.
Li, Yongle
Guo, Hua
Suleimanov, Yury V.
Alternative Title
Communication: Full dimensional quantum rate coefficients and kinetic isotope effects from ring polymer molecular dynamics for a seven-atom reaction OH + CH[subscript 4] → CH[subscript 3] + H[subscript 2]O
Date Issued
June 2013
Journal
The Journal of Chemical Physics
Publisher
American Institute of Physics (AIP)
Citation
Allen, Joshua W., William H. Green, Yongle Li, Hua Guo, and Yury V. Suleimanov. “Communication: Full Dimensional Quantum Rate Coefficients and Kinetic Isotope Effects from Ring Polymer Molecular Dynamics for a Seven-Atom Reaction OH + CH[subscript 4] → CH[subscript 3] + H[subscript 2]O.” The Journal of Chemical Physics 138, no. 22 (2013): 221103.
Version
Author's final manuscript
Abstract
The kinetic isotope effect (KIE) of the seven-atom reactions OH + CH[subscript 4] → CH[subscript 3] + H[subscript 2]O and OH + CD[subscript 4] → CD[subscript 3] + HDO over the temperature range 200–1000 K is investigated using ring polymer molecular dynamics (RPMD) on a full-dimensional potential energy surface. A comparison of RPMD with previous theoretical results obtained using transition state theory shows that RPMD is a more reliable theoretical approach for systems with more than 6 atoms, which provides a predictable level of accuracy. We show that the success of RPMD is a direct result of its independence of the choice of transition state dividing surface, a feature that is not shared by any of the transition state theory-based methods. Our results demonstrate that RPMD is a prospective method for studies of KIEs for polyatomic reactions for which rigorous quantum mechanical calculations are currently impossible.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Terms of Use
Creative Commons Attribution-Noncommercial-Share Alike
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1063/1.4811329
