摘要
本文基于从头算的结果,对HO-H_2(D_2)→H_2O(HOD)—H(D)反应的热力学和动力学进行了理论研究,分析了各种因素对计算结果的影响,并给出了一套完整的热、动力学参数.计算结果与现有的实验数据符合很好,在较低温度下,速率常数服从Arrhenius方程,较宽温度区间有非Arrhenius行为.
We have carried out thermodynamic and kinetic calculations basing on the results of ab initio quantum chemistry for the reaction HO + H2(D2)→H2O(HOD)+H(D). The factors affecting the exactitude of the calculations have been found out. A set of exact thermodynamic functions and kinetic parameters is presented. The calculated results are in good agreement with available experimental data over a broad temperature range. The rate constants predicted by transition state theory exhibit non-Arrhenius behavior in a wide temperature range, but can be described by Arrhenius expressions at low temperature. The theoritial effective activation energy is just the same as the best experimental value.
