title: Quantum rate coefficients and kinetic isotope effect for the reaction Cl + CH4 → HCl + CH3 from ring polymer molecular dynamics.
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.
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Yongle
authors.initials: Y
authors.lastname: Li
authors.forename: Yury V
authors.initials: YV
authors.lastname: Suleimanov
authors.forename: William H
authors.initials: WH
authors.lastname: Green
authors.forename: Hua
authors.initials: H
authors.lastname: Guo
mesh_terms: D002712:Chlorides / Q000737:chemistry*; D006851:Hydrochloric Acid / Q000737:chemistry*; D007700:Kinetics; D008697:Methane / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011108:Polymers / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D002712:Chlorides; D011108:Polymers; D008697:Methane; D006851:Hydrochloric Acid