Quantum rate coefficients and kinetic isotope effect for the reaction Cl + CH4 → HCl + CH3 from ring polymer molecular dynamics

J Phys Chem A. 2014 Mar 20;118(11):1989-96. doi: 10.1021/jp501043z. Epub 2014 Mar 7.

Abstract

Thermal rate coefficients and kinetic isotope effect have been calculated for prototypical heavy-light-heavy polyatomic bimolecular reactions Cl + CH4/CD4 → HCl/DCl + CH3/CD3, 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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Chlorides / chemistry*
  • Hydrochloric Acid / chemistry*
  • Kinetics
  • Methane / chemistry*
  • Molecular Dynamics Simulation*
  • Polymers / chemistry*
  • Quantum Theory*

Substances

  • Chlorides
  • Polymers
  • Methane
  • Hydrochloric Acid