Ab initio kinetics for decomposition/isomerization reactions of C 2H5O radicals

Zhen Feng Xu, Kun Xu, Ming-Chang Lin

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28 Scopus citations

Abstract

The ground-state potential energy surface of the C2H 5O system, including the decomposition and isomerization of the ethoxy (CH3CH2O), 1-hydroxyethyl (CH3CHOH), and 2-hydroxyethyl (CH2CH2OH) radicals, is computed by the modified Gaussian-2 (G2M) and CCSD(T)/6-311 +G(3df,2p) methods by using the geometries optimized at the B3LYP/6-311 + G(3df,2p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the unimolecular isomerization and decomposition reactions of the three radicals by the microcanonical transition-state theory and Rice-Ramsperger-Kassel-Marcus (RRKM) theory in the temperature range of 200-3000 K at varying pressures of He and other diluents. The predicted rate constants are in reasonable agreement with the available experimental data, in addition, the predicted heats of formation of the three isomeric radicals are compared with available experimental and theoretical values.

Original languageEnglish
Pages (from-to)972-982
Number of pages11
JournalChemPhysChem
Volume10
Issue number6
DOIs
StatePublished - 14 Apr 2009

Keywords

  • Ab initio calculations
  • Isomerization
  • Kinetics
  • Radical reactions
  • Transition states

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