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Kinetics of the hydrogen abstraction CHO + Alkane → HCHO + Alkyl reaction class: an application of the reaction class transition state theory

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Abstract

The kinetics of the hydrogen abstraction at alkanes by formyl radicals is investigated using the reaction class transition state theory (RC-TST) approach combined with the linear energy relationship (LER) or the barrier height grouping (BHG). The rate constants of a reaction in this class can be estimated through those of the reference reaction, CHO + C2H6, which are obtained from rate constants of the reaction that involves the smallest species, namely CHO + CH4, using the explicit RC-TST scaling. The thermal rate constants of this smallest reaction are evaluated at the canonical variational transition state theory (CVT) with the corrections from the small-curvature tunneling (SCT) and hindered rotation (HR) treatments. Our analyses indicate that less than 40% systematic errors, on the average, exist in the predicted rate constants using both the LER approach, where only reaction energy is needed, and the BHG approach, where no additional information is needed; while comparing to explicit rate calculations the differences are less than 60%.

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Authors and Affiliations

  1. Department of Chemistry, University of Utah, 315 S. 1400 E. Rm. 2020, Salt Lake City, UT, 84112, USA

    Lam K. Huynh & Thanh N. Truong

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  1. Lam K. Huynh
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  2. Thanh N. Truong
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Correspondence to Thanh N. Truong.

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Contribution to Mark S. Gordon 65th Birthday Festschrift Issue.

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Huynh, L.K., Truong, T.N. Kinetics of the hydrogen abstraction CHO + Alkane → HCHO + Alkyl reaction class: an application of the reaction class transition state theory. Theor Chem Account 120, 107–118 (2008). https://doi.org/10.1007/s00214-007-0311-9

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  • DOI: https://doi.org/10.1007/s00214-007-0311-9

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