Chemistry Institute, University of Bialystok, Hurtowa 1, 15-399 Bialystok, Poland.
J Phys Chem A. 2012 Jan 12;116(1):242-54. doi: 10.1021/jp208432z. Epub 2011 Dec 20.
Kinetics of the 1,5-intramolecular hydrogen migration in the alkyl radicals reaction class has been studied using the reaction class transition state theory combined with the linear energy relationship (LER) and the barrier height grouping (BHG) approach. The high pressure limits of the rate constants for the reference reaction of 1-pentyl → 1-pentyl, calculated by the Canonical Variational Transition State Theory (CVT) with the Small Curvature Tunneling (SCT), are taken from the literature. Direct comparison with available experimental data indicates that the RC-TST/LER, where only reaction energy 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 when compared to explicit rate calculations.
使用反应类别过渡态理论结合线性能量关系（LER）和势垒高度分组（BHG）方法，研究了烷基自由基反应类中 1,5-分子内氢迁移的动力学。通过小曲率隧道（SCT）的正则变分过渡态理论（CVT）计算的参考反应 1-戊基→1-戊基的速率常数的高压极限取自文献。与可用的实验数据进行直接比较表明，仅需要反应能的 RC-TST/LER 可以非常准确地预测该反应类中的任何反应的速率常数。具体对于这个反应类别，与明确的速率计算相比，RC-TST/LER 方法在预测的速率常数中系统误差小于 65%。
