论文标题
还使用条件能概率的化学速率常数还原论的方法
Reductionist approach to chemical rate constants using conditional energy probabilities
论文作者
论文摘要
不同的速率理论产生了与现象学ARRHENIUS定律一致的相似形式的速率常数，尽管它们来自物理学的各个分支，包括经典的热力学，统计和量子力学。这种融合支持Arrhenius定律的有效性，但也表明存在更简单的基本原则。这里提出了一种还原的方法，其中能量指数因子是足够能量的有条件概率，而指数的前一个因子是有利于反应的构型复发的频率，本身与混乱系统中的配置概率成正比。这种极简主义的虽然严格的数学方法使得绕过某些可疑的假设对更复杂的理论，并阐明了所使用的不同能量的含义：激活能量，阈值能量和化学能。
Different rate theories yielded similar forms of rates constants consistent with the phenomenological Arrhenius law, although they were derived from various branches of physics including classical thermodynamics, statistical and quantum mechanics. This convergence supports the validity of the Arrhenius law but also suggests the existence of an even simpler underlying principle. A reductionnist approach is proposed here in which the energetic exponential factor is a conditional probability of sufficient energy and the pre-exponential factor is the frequency of recurrence of the configuration favorable to the reaction, itself proportional to a configurational probability in a chaotic system. This minimalist while rigorous mathematical approach makes it possible to bypass certain questionable postulates of more sophisticated theories and clarifies the meaning of the different types of energies used: activation energy, threshold energy and chemical energy.
