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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetics of 1,4-Hydrogen Migration in the Alkyl Radical Reaction Class
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Kinetics of 1,4-Hydrogen Migration in the Alkyl Radical Reaction Class

机译：烷基自由基反应类别中1,4-氢迁移的动力学

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摘要

The kinetics of the 1,4-intramolecular hydrogen migration in the alkyl radicals reaction class has been studied using reaction class transition-state theory combined with the linear energy relationship (LER) and barrier height grouping (BHG) approach. The rate constants for the reference reaction of n-C4H9 were obtained by canonical variational transition-state theory (CVT) with the small curvature tunnelling (SCT) correction in the temperature range 300-3000 K with potential-energy surface information computed at the CCSD(T)/cc-pVDZ//BH&HLYP/cc-pVDZ level of theory. Error analyses indicate that RC-TST/LER, where only reaction energy is needed, and RC-TST/BHG, where no other information is needed, can predict rate constants for any reaction in this reaction class with excellent accuracy. Specifically, for this reaction class the RC-TST/LER method has less than 65% systematic errors in the predicted rate constants, while the RC-TST/BHG method has less than 80% error when compared to explicit rate calculations.
机译：结合线性能级关系（LER）和势垒高度分组（BHG）方法，研究了反应级过渡态理论对烷基自由基反应级中1,4-分子氢迁移的动力学进行了研究。 n-C4H9参考反应的速率常数是通过标准变分过渡态理论（CVT）和小曲率隧穿（SCT）校正在300-3000 K的温度范围内获得的，并通过CCSD计算了势能表面信息（T）/ cc-pVDZ // BH＆HLYP / cc-pVDZ理论水平。误差分析表明，仅需要反应能量的RC-TST / LER和不需要其他信息的RC-TST / BHG可以非常精确地预测此反应类别中任何反应的速率常数。具体而言，对于该反应类别，与显式速率计算相比，RC-TST / LER方法的预测速率常数的系统误差小于65％，而RC-TST / BHG方法的预测误差的系统误差小于80％。

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