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Title: Nonthermal rate constants for CH 4* + X → CH 3 + HX, X = H, O, OH, and O 2

Abstract

Quasiclassical trajectories are essential to compute nonthermal rate constants, k*, for abstraction reactions involving highly-excited methane CH 4* and the radicals H, O, OH, and O 2. Several temperatures and internal energies of methane, E vib, are observed, and significant nonthermal rate enhancements for large E vib are found. Specifically, when CH 4* is internally excited close to its dissociation threshold (E vib approximate to D 0 = 104 kcal/mol), its reactivity with H, O, and OH is shown to be collision-rate-limited and to approach that of comparably-sized radicals, such as CH 3, with k* > 10 -10 cm 3 molecule -1 s -1. Rate constants this large are more typically associated with barrierless reactions, and at 1000 K, this represents a nonthermal rate enhancement, k*/k, of more than two orders of magnitude relative to thermal rate constants k. We show that large nonthermal rate constants persist even after significant internal cooling, with k*/k > 10 down to E vib approximate to D 0/4. The competition among collisional cooling and nonthermal reactivity is studied using a simple model, and nonthermal reactions are shown to account for up to 35%-50% of the fate of the products of H + CH 3more » = CH 4* under conditions of practical relevance to combustion. Lastly, the accuracy of an effective temperature model for estimating k* from k is quantified.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1510465
Alternate Identifier(s):
OSTI ID: 1502269
Grant/Contract Number:  
AC02-06CH11357; FWP 59044
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 11; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jasper, Ahren W., Sivaramakrishnan, Raghu, and Klippenstein, Stephen J. Nonthermal rate constants for CH4* + X → CH3 + HX, X = H, O, OH, and O2. United States: N. p., 2019. Web. doi:10.1063/1.5090394.
Jasper, Ahren W., Sivaramakrishnan, Raghu, & Klippenstein, Stephen J. Nonthermal rate constants for CH4* + X → CH3 + HX, X = H, O, OH, and O2. United States. doi:10.1063/1.5090394.
Jasper, Ahren W., Sivaramakrishnan, Raghu, and Klippenstein, Stephen J. Thu . "Nonthermal rate constants for CH4* + X → CH3 + HX, X = H, O, OH, and O2". United States. doi:10.1063/1.5090394.
@article{osti_1510465,
title = {Nonthermal rate constants for CH4* + X → CH3 + HX, X = H, O, OH, and O2},
author = {Jasper, Ahren W. and Sivaramakrishnan, Raghu and Klippenstein, Stephen J.},
abstractNote = {Quasiclassical trajectories are essential to compute nonthermal rate constants, k*, for abstraction reactions involving highly-excited methane CH4* and the radicals H, O, OH, and O2. Several temperatures and internal energies of methane, Evib, are observed, and significant nonthermal rate enhancements for large Evib are found. Specifically, when CH4* is internally excited close to its dissociation threshold (Evib approximate to D0 = 104 kcal/mol), its reactivity with H, O, and OH is shown to be collision-rate-limited and to approach that of comparably-sized radicals, such as CH3, with k* > 10-10 cm3 molecule-1 s-1. Rate constants this large are more typically associated with barrierless reactions, and at 1000 K, this represents a nonthermal rate enhancement, k*/k, of more than two orders of magnitude relative to thermal rate constants k. We show that large nonthermal rate constants persist even after significant internal cooling, with k*/k > 10 down to Evib approximate to D0/4. The competition among collisional cooling and nonthermal reactivity is studied using a simple model, and nonthermal reactions are shown to account for up to 35%-50% of the fate of the products of H + CH3 = CH4* under conditions of practical relevance to combustion. Lastly, the accuracy of an effective temperature model for estimating k* from k is quantified.},
doi = {10.1063/1.5090394},
journal = {Journal of Chemical Physics},
number = 11,
volume = 150,
place = {United States},
year = {2019},
month = {3}
}

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