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Issue 1, 2020
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An accurate potential energy surface and ring polymer molecular dynamics study of the Cl + CH4 → HCl + CH3 reaction

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Abstract

The reaction Cl + CH4 → HCl + CH3, a prototypical bimolecular reaction, has been established as an important proving ground for studying chemical reaction kinetics and dynamics of polyatomic molecules. In this work, a globally accurate full-dimensional potential energy surface (PES) for this reaction is developed by using the permutationally invariant polynomial neural network (PIP-NN) approach based on 74 000 points calculated at the level of the explicitly correlated unrestricted coupled cluster single, double, and perturbative triple level with the augmented correlation corrected valence triple-zeta basis set (UCCSD(T)-F12a/AVTZ). For points in the entrance channel, spin–orbit corrections stemming from Cl(2P) are determined at the level of complete active space self-consistent field (CASSCF) with the AVTZ basis set. With this PES, thermal rate coefficients and kinetic isotope effects are computed for reactions Cl + CH4 → HCl + CH3 and Cl + CD4 → DCl + CD3 using the ring polymer molecular dynamics (RPMD) method, which can provide reliable estimations for thermal rate coefficients effectively. Generally, the agreement with the scattered experimental results is reasonably satisfactory.

Graphical abstract: An accurate potential energy surface and ring polymer molecular dynamics study of the Cl + CH4 → HCl + CH3 reaction

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Article information


Submitted
19 Oct 2019
Accepted
30 Nov 2019
First published
02 Dec 2019

Phys. Chem. Chem. Phys., 2020,22, 344-353
Article type
Paper

An accurate potential energy surface and ring polymer molecular dynamics study of the Cl + CH4 → HCl + CH3 reaction

Y. Liu and J. Li, Phys. Chem. Chem. Phys., 2020, 22, 344
DOI: 10.1039/C9CP05693A

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