A theoretical analysis of the CH{sub 3} + H reaction : isotope effects, the high pressure limit, and transition state recrossing. Metadata

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Title

  • Main Title A theoretical analysis of the CH{sub 3} + H reaction : isotope effects, the high pressure limit, and transition state recrossing.

Creator

  • Author: Klippenstein, S. J.
    Creator Type: Personal
  • Author: Georgievskii, Y.
    Creator Type: Personal
  • Author: Harding, L.
    Creator Type: Personal

Contributor

  • Sponsor: United States. Department of Energy.
    Contributor Type: Organization
    Contributor Info: US Department of Energy (United States)

Publisher

  • Name: Argonne National Laboratory
    Place of Publication: Illinois
    Additional Info: Argonne National Lab., IL (United States)

Date

  • Creation: 2001-12-20

Language

  • English

Description

  • Content Description: The reaction of methyl radicals with hydrogen atoms is studied with a combination of ab initio quantum chemistry, variational transition state theory, and classical trajectory simulations. The interaction between the two radicals, including the umbrella mode of the methyl radical, is examined at the CAS+1+2 level using an augmented correlation consistent polarized valence triple zeta basis set. The implementation of an analytic representation of the ab initio data within variable reaction coordinate transition state theory yields predictions for the zero-pressure limit isotopic exchange rate constants that are about 15% greater than the available experimental data. Trajectory simulations indicate that the transition state recrossing factor for the capture process is 0.90, essentially independent of temperature and isotope. The dynamically corrected theoretical prediction for the CH{sub 3} + H high pressure rate coefficient is well reproduced by the expression 1.32 x 10{sup -10}T{sup 0.153}exp(-15.1/RT) cm{sup 3}molecule{sup -1}s{sup -1}, where R = 1.987 cal mole{sup -1} K{sup -1}, for temperatures between 200 and 2400 K. This prediction is in good agreement with the converted experimental data for all but the one measurement at 200 K. Calculations for the triplet abstraction channel suggest that it is unimportant. Methyl umbrella mode variations have surprisingly little effect on the predicted rate coefficients.
  • Physical Description: vp.

Subject

  • Keyword: Isotopic Exchange
  • Keyword: Combustion
  • Keyword: Forecasting
  • STI Subject Categories: 08 Hydrogen
  • Keyword: Implementation
  • Keyword: Atoms
  • Keyword: Radicals
  • Keyword: Valence
  • Keyword: Methyl Radicals
  • Keyword: Chemistry
  • Keyword: Triplets
  • Keyword: Isotope Effects
  • Keyword: Hydrogen

Source

  • Conference: 29th International Symposium on Combustion, Sapporo (JP), 07/21/2002--07/26/2002

Collection

  • Name: Office of Scientific & Technical Information Technical Reports
    Code: OSTI

Institution

  • Name: UNT Libraries Government Documents Department
    Code: UNTGD

Resource Type

  • Article

Format

  • Text

Identifier

  • Report No.: ANL/CHM/CP-106499
  • Grant Number: W-31-109-ENG-38
  • Office of Scientific & Technical Information Report Number: 799817
  • Archival Resource Key: ark:/67531/metadc736237
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