Kinetics Study of the OH + Alkene H2O + Alkenyl Reaction Class

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• 作者：Lam K. Huynh ; Kyle Barriger ; Angela Violi
• 刊名：Journal of Physical Chemistry A
• 出版年：2008
• 出版时间：February 21, 2008
• 年：2008
• 卷：112
• 期：7
• 页码：1436 - 1444
• 全文大小：273K
• 年卷期：v.112,no.7(February 21, 2008)
• ISSN：1520-5215

文摘

In this paper we report on the kinetics of hydrogen abstraction for the OH + alkene reaction class, using thereaction class transition state theory (RC-TST) combined with the linear energy relationship (LER) and thebarrier height grouping (BHG) approaches. Parameters for the RC-TST were derived from theoreticalcalculations using a set of 15 reactions representing the hydrogen abstractions from the terminal and nonterminalcarbon sites of the double bond of alkene compounds. Both the RC-TST/LER, where only reaction energy isneeded at either density functional theory BH&HLYP or semiempirical AM1 levels, and RC-TST/BHG,where no additional information is required, are found to be promising methods for predicting rate constantsfor a large number of reactions in this reaction class. Detailed error analyses show that, when compared toexplicit theoretical calculations, the averaged systematic errors in the calculated rate constants using both theRC-TST/LER and RC-TST/BHG methods are less than 25% in the temperature range 300-3000 K. Theestimated rate constants using these approaches are in good agreement with available data in the literature.