摘要
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O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.
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, kA, (E) and kA'(E) respectively, have also been studied. The calculations show that kA,(E) is larger than kA,, (E), and that the two constants tend to consistent with the increase in energy.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
1995年第4期323-327,共5页
Acta Chimica Sinica
基金
国家自然科学基金资助的项目
