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

Content Provider	Semantic Scholar
Author	Li, Yongle Suleimanov, Yury V. Green, William H.
Copyright Year	2014
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.
File Format	PDF HTM / HTML
PubMed reference number	24558961
Journal	Medline
Volume Number	118
Issue Number	11
Alternate Webpage(s)	http://dspace.mit.edu/openaccess-disseminate/1721.1/95491
Alternate Webpage(s)	https://dspace.mit.edu/bitstream/handle/1721.1/95491/5.pdf?isAllowed=y&sequence=3
Alternate Webpage(s)	https://doi.org/10.1021/jp501043z
Journal	The journal of physical chemistry. A
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article