Rate coefficients of the reactions of isopentane with H and CH3 radicals: Quantum mechanical approach

Xin Hong, Hongyan Sun, Chung K. Law

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Abstract

The rate coefficients of the H-abstraction reactions of isopentane by H and CH3 radicals were determined by transition state theory (TST) and canonical variational transition state theory (CVT) with the potential energy surfaces calculated at the CBS-QB3 and G3B3 levels, and with the quantum mechanical tunneling effect corrected using the small-curvature tunneling (SCT) and Eckart methods. It was found that the G3B3 method predicts good barrier heights for the reactions of isopentane + H radical, and that the CBS-QB3 method predicts good barrier heights for the reactions of isopentane + CH3 radical. Furthermore, the energy barriers for the abstraction of primary, secondary, and tertiary hydrogen of isopentane were found to be consistent with the corresponding H-bond dissociation energies derived by the enthalpy difference between the C5H11 radical + H and isopentane. By using isodesmic reaction analysis, the enthalpies of formation (ΔHof 298) of the four initial H-abstraction radical products of isopentane C.H2CH2CH(CH3)CH3, CH3CH2CH(CH3)C.H2, CH3C.HCH(CH3)CH3, and CH3CH2C.(CH3)CH3 were determined to be 12.0, 11.9, 9.4, and 7.0 kcal mol-1, respectively. To account for quantum mechanical tunneling effects, the rate coefficients corrected by the SCT method were found to be closer to the experimental data than those by the Eckart method. Thermal rate coefficients for the abstraction of primary, secondary, and tertiary hydrogen atom within isopentane by H and CH3 radicals in the temperature range of 300- 1500 K were determined and also compared with available experimental data and theoretical results.

Original languageEnglish (US)
Pages (from-to)357-364
Number of pages8
JournalComputational and Theoretical Chemistry
Volume963
Issue number2-3
DOIs
StatePublished - Feb 2011

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Keywords

  • DFT and ab initio
  • H-abstraction
  • Isopentane
  • Rate coefficients
  • Small-curvature tunneling correction

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