论文部分内容阅读
以过渡状态理论为基础，研究了单分子振动选模反应的微正则系综速率常数的计算方法．在计算中考虑了量子力学隧道效应校正及振动对沿IRC运动的耦合作用校正．以反应C＝CH（F）→HC≡CF的氢迁移反应和C＝CF2→FC≡CF的氟迁移反应为例，研究了它们的面外振动选模反应的速率常数．结果表明，这两个反应在低能区有明显的选模性，在高能区选模性减弱．
Based on the transition state theory, the method of calculating the canonical ensemble rate constant of a single-molecule vibrational mode reaction is studied. In the calculation, quantum mechanics tunneling correction and coupling correction of vibration along IRC motion are considered. Taking the hydrogen transfer reaction of C = CH (F) → HC≡CF and the fluorine transfer reaction of C = CF2 → FC≡CF as an example, the rate constants of their out-of-plane vibration mode selection reaction are studied. The results show that these two reactions have obvious mode selection in the low-energy region and weakening of the mode selection in the high-energy region.