Jump to main content
Jump to site search

Issue 29, 2017
Previous Article Next Article

Kinetics study of the CN + CH4 hydrogen abstraction reaction based on a new ab initio analytical full-dimensional potential energy surface

Author affiliations

Abstract

We have developed an analytical full-dimensional potential energy surface, named PES-2017, for the gas-phase hydrogen abstraction reaction between the cyano radical and methane. This surface is fitted using high-level ab initio information as input. Using the PES-2017 surface, a kinetics study was performed via two theoretical approaches: variational transition-state theory with multidimensional tunnelling (VTST-MT) and ring polymer molecular dynamics (RPMD). The results are compared with the experimental data. In the whole temperature range analysed, 300–1500 K, both theories agree within a factor of <2, reproducing the experimental behaviour taking into account the experimental uncertainties. At high temperatures, where the recrossing effects dominate and the RPMD theory is exact, both theories differ by a factor of about 20%; while at low temperatures this difference is larger, 45%. Note that in this temperature regime, the tunnelling effect is negligible. The CN + CH4/CD4 kinetic isotope effects are important, reproducing the scarce experimental evidence. The good agreement with the ab initio information used in the fitting process (self-consistency test) and with the kinetic behaviour in a wide temperature range gives confidence and strength to the new surface.

Graphical abstract: Kinetics study of the CN + CH4 hydrogen abstraction reaction based on a new ab initio analytical full-dimensional potential energy surface

Back to tab navigation

Publication details

The article was received on 24 May 2017, accepted on 27 Jun 2017 and first published on 28 Jun 2017


Article type: Paper
DOI: 10.1039/C7CP03499G
Citation: Phys. Chem. Chem. Phys., 2017,19, 19341-19351
  •   Request permissions

    Kinetics study of the CN + CH4 hydrogen abstraction reaction based on a new ab initio analytical full-dimensional potential energy surface

    J. Espinosa-Garcia, C. Rangel and Y. V. Suleimanov, Phys. Chem. Chem. Phys., 2017, 19, 19341
    DOI: 10.1039/C7CP03499G

Search articles by author

Spotlight

Advertisements