氟代乙炔氢迁移反应微正则系综速率常数的计算

以氟代乙炔的氢迁移反应为例, 计算了隧道效应、曲率因子和转动选态对微正则系综单分子反应速率常数的影响。结果表明, 在低能区域, 隧道效应和曲率因子对反应速率有较大影响, 均使反应速率增加, 而在高能区域作用不明显。与此同时还研究了不同对称态下的反应速率常数, 结果表明, 本例中的两对称态(A'态和A"态)的反应速率常数在能量较低时差异较大, 随能量升高, 两者趋于相等。

Calculation of the microcanonical rate constants for the hydrogen-transfer reaction of fluoro substituted acetylene

The hydrogen-transfer reaction of HC≡CF→C=H(F) was taken as an example to calculate the microcanonical unimolecular rate constants with consideration of the tunneling correction and the curvature correction and the selection of the rotation states. The results indicate that the tunneling and the curvature increase much obviously the reaction rate constants in the lower energy regions than in the heigher regions. The rate constants in A' and A" symmetry, k~A'(E) and k~A"(E) respectively, have also been studied. The calculations show that k~A'(E) is larger than k~A"(E), and that the two constants tend to consistent with the increase in enrgy.