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Phase space structures causing the reaction rate decrease in the collinear hydrogen exchange reaction
Journal of Mathematical Chemistry ( IF 1.7 ) Pub Date : 2019-11-25 , DOI: 10.1007/s10910-019-01083-4
Vladimír Krajňák , Holger Waalkens

The collinear hydrogen exchange reaction is a paradigm system for understanding chemical reactions. It is the simplest imaginable atomic system with 2 degrees of freedom modeling a chemical reaction, yet it exhibits behaviour that is still not well understood—the reaction rate decreases as a function of energy beyond a critical value. Using lobe dynamics we show how invariant manifolds of unstable periodic orbits guide trajectories in phase space. From the structure of the invariant manifolds we deduce that insufficient transfer of energy between the degrees of freedom causes a reaction rate decrease. In physical terms this corresponds to the free hydrogen atom repelling the whole molecule instead of only one atom from the molecule. We further derive upper and lower bounds of the reaction rate, which are desirable for practical reasons.

中文翻译:

导致共线氢交换反应中反应速率降低的相空间结构

共线氢交换反应是理解化学反应的范式系统。它是可以想象到的最简单的原子系统,具有 2 个自由度模拟化学反应,但它表现出的行为仍未得到很好的理解——反应速率随着能量的增加而降低,超过临界值。我们使用叶瓣动力学展示了不稳定周期轨道的不变流形如何引导相空间中的轨迹。根据不变流形的结构,我们推断自由度之间的能量传递不足导致反应速率降低。在物理术语中,这对应于自由氢原子排斥整个分子而不是分子中的一个原子。我们进一步推导出反应速率的上限和下限,这出于实际原因是可取的。
更新日期:2019-11-25
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