变分过渡态理论对H+H_2及其同位素选态反应的研究

Studies on the State-Selected Reaction of H+H2(v) and Its Isotopic Analogues by Variational Transition State Theory

将选态速度常数的计算推广到任意指定反应物、过渡态的振动激发态.用此法计算了H+H_2(v)及其同位素经不同振动激发过渡态时的速度常数,发现弯曲振动模激发所得结果与实验值更符合,并且在给定能量下,过渡态的弯曲振动模激发比其对称伸缩模激发更有利于反应进行.

In this paper, the variational transition state theory is extended to calculate the state-selected reaction rate constants for an arbitrarily assigned vibrational excited reactants and their transition state. The extended theory can be used to calculate the rate constants for a series reactions of H+H2 (v) and its isotopic analogues through different vibrational excited transition states. In comparison of the calculated results with experimental values, it is found that the results obtained by the exciting bend vibration modes are nuch close to the experimental values. It is also first obtained that when an energy is given, the exciting transition state's bend modes are more favourable to the reactions than the exciting stretch ones.