Thermal Rate Coefficients via Variational Transition State Theory for the Unimolecular Decomposition/Isomerization of 1-Pentyl Radical: Ab Initio and Direct Dynamics Calculations.

Luminita C. Jitariu, Lee D. Jones, Struan H. Robertson, Michael J. Pilling, Ian H. Hillier

    Research output: Contribution to journalArticlepeer-review

    Abstract

    Calcns. of thermal rates for the reactions of the isomeric pentyl radicals involving (1,2), (1,3), (1,4), and (1,5) intramol. H-atom transfer, C-C bond scission, and H-atom elimination have been carried out. Potential energy surfaces and assocd. properties for these reactions have been used for direct dynamics studies within conventional and variational transition state theory formalism including nonclassical effects, using the dual-level technique (PUMP-SAC2/6-311G**///AM1). We found that for C-C scission, the barrier is broad, and a significant tightening of the loose transition state reduces the rate coeffs. across a wide temp. range. Converse behavior is predicted for the isomerization reactions where the optimal combination of a low effective mass with a narrow barrier opens the best tunneling paths. High-pressure limiting rate coeffs. and kinetic parameters obtained in this study show good agreement with exptl. measurements and previous theor. work. [on SciFinder (R)]
    Original languageEnglish
    Pages (from-to)8607-8617
    Number of pages10
    JournalJournal of Physical Chemistry A
    Volume107
    Issue number41
    DOIs
    Publication statusPublished - 12 Sept 2003

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