Kinetics of the hydrogen abstraction OH plus alkane→H2O plus alkyl reaction class: An application of the reaction class transition state theory
Kinetics of the hydrogen abstraction OH plus alkane→H2O plus alkyl reaction class: An application of the reaction class transition state theory
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DOI：
10.1021/jp051280d
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发表时间：
2006-01-19
影响因子：
2.9
通讯作者：
Truong, TN
中科院分区：
文献类型：
--
作者：
Huynh, LK;Ratkiewicz, A;Truong, TN
本文应用反应类过渡态理论（RC-TST）预测了OH +烷烃-> HOH +烷基夺氢反应的热速率常数。我们已经推导出的所有参数的RC-TST方法为这类反应的速率常数的19个代表性的反应，耦合与线性能量关系（LER），使速率常数在这类中的任何反应可以预测从它的反应能量计算在AM I半经验或BH&HLYP/cc-pVDZ理论水平。所选反应的RC-TST/LER热速率常数与文献中的结果吻合得很好。结果表明，RC-TST/LER方法是一种有效的方法，可以准确地估计大量此类反应的速率常数。LER的分析导致发现P-碳自由基稳定化效应，其稳定该类中产生具有一个或多个P-碳的产物的任何反应的过渡态。因此导致这种反应的势垒较低。
This paper presents an application of the reaction class transition state theory (RC-TST) to predict thermal rate constants for hydrogen abstraction reactions of the type OH + alkane -> HOH + alkyl. We have derived all parameters for the RC-TST method for this reaction class from rate constants of 19 representative reactions, coupling with linear energy relationships (LERs), so that rate constants for any reaction in this class can be predicted from its reaction energy calculated at either the AM I semiempirical or BH&HLYP/cc-pVDZ level of theory. The RC-TST/LER thermal rate constants for selected reactions are in good agreement with those available in the literature. Detailed analyses of the results show that the RC-TST/LER method is an efficient method for accurately estimating rate constants for a large number of reactions in this class. Analysis of the LERs leads to the discovery of the P-carbon radical stabilization effect that stabilizes the transition state of any reaction in this class that yields products having one or more P-carbons. and thus leads to the lower barrier for such a reaction.