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Title: Potential energy surface, thermal, and state-selected rate coefficients, and kinetic isotope effects for Cl+CH{sub 4}{yields}HCl+CH{sub 3}

Abstract

A new potential energy surface is reported for the gas-phase reaction Cl+CH{sub 4}{yields}HCl+CH{sub 3}. It is based on the analytical function of Jordan and Gilbert for the analog reaction H+CH{sub 4}{yields}H{sub 2}+CH{sub 3}, and it is calibrated by using the experimental thermal rate coefficients and kinetic isotope effects. The forward and reverse thermal rate coefficients were calculated using variational transition state theory with semiclassical transmission coefficients over a wide temperature range, 200-2500 K. This surface is also used to analyze dynamical features, such as reaction-path curvature, the coupling between the reaction coordinate and vibrational modes, and the effect of vibrational excitation on the rate coefficients. We find that excitation of C-H stretching modes and Cl-H stretching modes enhances the rate of both the forward and the reverse reactions, and excitation of the lowest frequency bending mode in the CH{sub 4} reactant also enhances the rate coefficient for the forward reaction. However, the vibrational excitation of the CH{sub 3} umbrella mode (lowest frequency mode in products) slows the reaction at temperatures below 1000 K, while above 1000 K it also accelerates the reaction. (c) 2000 American Institute of Physics.

Authors:
 [1];  [2];  [1]
  1. Departamento de Quimica Fisica, Facultad de Ciencias, Universidad de Extremadura, 06071 Badajoz, (Spain)
  2. Department of Chemistry and Supercomputer Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431 (United States)
Publication Date:
OSTI Identifier:
20216527
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 112; Journal Issue: 21; Other Information: PBD: 1 Jun 2000; Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHEMICAL REACTION KINETICS; CHLORINE; METHANE; ISOTOPE EFFECTS; POTENTIAL ENERGY; TEMPERATURE RANGE 1000-4000 K; TEMPERATURE RANGE 0400-1000 K; TEMPERATURE RANGE 0273-0400 K; VIBRATIONAL STATES; METHYL RADICALS; EXPERIMENTAL DATA; THEORETICAL DATA

Citation Formats

Corchado, J. C., Truhlar, D. G., and Espinosa-Garcia, J. Potential energy surface, thermal, and state-selected rate coefficients, and kinetic isotope effects for Cl+CH{sub 4}{yields}HCl+CH{sub 3}. United States: N. p., 2000. Web. doi:10.1063/1.481602.
Corchado, J. C., Truhlar, D. G., & Espinosa-Garcia, J. Potential energy surface, thermal, and state-selected rate coefficients, and kinetic isotope effects for Cl+CH{sub 4}{yields}HCl+CH{sub 3}. United States. doi:10.1063/1.481602.
Corchado, J. C., Truhlar, D. G., and Espinosa-Garcia, J. Thu . "Potential energy surface, thermal, and state-selected rate coefficients, and kinetic isotope effects for Cl+CH{sub 4}{yields}HCl+CH{sub 3}". United States. doi:10.1063/1.481602.
@article{osti_20216527,
title = {Potential energy surface, thermal, and state-selected rate coefficients, and kinetic isotope effects for Cl+CH{sub 4}{yields}HCl+CH{sub 3}},
author = {Corchado, J. C. and Truhlar, D. G. and Espinosa-Garcia, J.},
abstractNote = {A new potential energy surface is reported for the gas-phase reaction Cl+CH{sub 4}{yields}HCl+CH{sub 3}. It is based on the analytical function of Jordan and Gilbert for the analog reaction H+CH{sub 4}{yields}H{sub 2}+CH{sub 3}, and it is calibrated by using the experimental thermal rate coefficients and kinetic isotope effects. The forward and reverse thermal rate coefficients were calculated using variational transition state theory with semiclassical transmission coefficients over a wide temperature range, 200-2500 K. This surface is also used to analyze dynamical features, such as reaction-path curvature, the coupling between the reaction coordinate and vibrational modes, and the effect of vibrational excitation on the rate coefficients. We find that excitation of C-H stretching modes and Cl-H stretching modes enhances the rate of both the forward and the reverse reactions, and excitation of the lowest frequency bending mode in the CH{sub 4} reactant also enhances the rate coefficient for the forward reaction. However, the vibrational excitation of the CH{sub 3} umbrella mode (lowest frequency mode in products) slows the reaction at temperatures below 1000 K, while above 1000 K it also accelerates the reaction. (c) 2000 American Institute of Physics.},
doi = {10.1063/1.481602},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 21,
volume = 112,
place = {United States},
year = {2000},
month = {6}
}