摘要
透过几率中考虑隧道效应而得到过渡态络合物振动、转动量子态的穿透系数,对弯曲振动态和转动态取统计平均就得到伸缩振动态的穿透系数,利用此穿透系数对传统的过渡态理论得到的反应速率常数做了修正.将反应速率常数的计算值与实验值比较发现:低温区(<300K)穿透系数修正的反应速率常数明显好于传统的过渡态理论的结果.
Transmission coefficients of vibrational states and rotational states of three-atom transition state complexes are got from the tunneling reactive probabilities. The vibrational transmission coefficients can be got by statistically averaging above transmission coefficients over bend vibrational states and rotational states. The conventional transition state theory is remedied by the transmission coefficient. It can be found from the comparison between the calculated values from remedied TST and the experiment values: the calculated rate constant values remedied by the transmission coefficients are better agreement with the experiment results than the those got from the conventional transition state theory within low temperature.
