Quantum Rate Coefficients and Kinetic Isotope Effect for the Reaction Cl + CH[subscript 4] → HCl + CH[subscript 3] from Ring Polymer Molecular Dynamics
Author(s)
Li, Yongle
Green, William H.
Guo, Hua
Suleymanov, Yury
Date Issued
February 2014
Journal
The Journal of Physical Chemistry A
Publisher
American Chemical Society (ACS)
Citation
Li, Yongle, Yury V. Suleimanov, William H. Green, and Hua Guo. “Quantum Rate Coefficients and Kinetic Isotope Effect for the Reaction Cl + CH[subscript 4] → HCl + CH[subscript 3] from Ring Polymer Molecular Dynamics.” The Journal of Physical Chemistry A 118, no. 11 (March 20, 2014): 1989–1996.
Version
Author's final manuscript
Abstract
Thermal rate coefficients and kinetic isotope effect have been calculated for prototypical heavy–light–heavy polyatomic bimolecular reactions Cl + CH[subscript 4]/CD[subscript 4] → HCl/DCl + CH[subscript 3]/CD[subscript 3], using a recently proposed quantum dynamics approach: ring polymer molecular dynamics (RPMD). Agreement with experimental rate coefficients, which are quite scattered, is satisfactory. However, differences up to 50% have been found between the RPMD results and those obtained from the harmonic variational transition-state theory on one of the two full-dimensional potential energy surfaces used in the calculations. Possible reasons for such discrepancy are discussed. The present work is an important step in a series of benchmark studies aimed at assessing accuracy for RPMD for chemical reaction rates, which demonstrates that this novel method is a quite reliable alternative to previously developed techniques based on transition-state theory.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Terms of Use
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Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/jp501043z
