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Publication Citation: Computational Study of the Reactions of Methane with XO Radicals (X = F, Cl, or Br): Implications in Combustion Chemistry

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Author(s): F Louis; Thomas C. Allison; Carlos A. Gonzalez; J P. Sawerysyn;
Title: Computational Study of the Reactions of Methane with XO Radicals (X = F, Cl, or Br): Implications in Combustion Chemistry
Published: May 01, 2001
Abstract: Theoretical calculations were carried out on the H-atom abstraction reaction from methane by XO (X = F, Cl or Br) radicals attack. Geometry optimizations and vibrational frequency calculations were performed using three methods: Moller-Plesset second-order perturbation theory (MP2), quadratic configuration interaction in the space of single and double excitations (QCISD), and the hybrid three-parameter exchange functional with Becke's non local exchange and Lee-Yang-Parr correlation functional (B3LYP). Single-point energy calculations were performed using several high quality basis sets. Canonical transition-state theory was used to perdict the rate constants as a function of temperature (700 - 2500K), and three-parameter Arrhenius expressions were obtained by fitting to the computed rate constants. The possible impact of the title reactions in combustion chemistry is also discussed.
Citation: Journal of Physical Chemistry A
Volume: 105
Issue: No. 17
Pages: pp. 4284 - 4289
Keywords: ab Initio;Arrhenius;Kinetics;rate constant
Research Areas: Thermophysics, Chemistry