Department of Physics, University of Liverpool, Liverpool L69 7ZE, United Kingdom.
School of Chemistry, University of Birmingham, Edgbaston B15 2TT, United Kingdom.
J Chem Phys. 2022 Aug 14;157(6):060901. doi: 10.1063/5.0098552.
Since Arrhenius first proposed an equation to account for the behavior of thermally activated reactions in 1889, significant progress has been made in our understanding of chemical reactivity. A number of capture theory models have been developed over the past several decades to predict the rate coefficients for reactions between ions and molecules-ranging from the Langevin equation (for reactions between ions and non-polar molecules) to more recent fully quantum theories (for reactions at ultracold temperatures). A number of different capture theory methods are discussed, with the key assumptions underpinning each approach clearly set out. The strengths and limitations of these capture theory methods are examined through detailed comparisons between low-temperature experimental measurements and capture theory predictions. Guidance is provided on the selection of an appropriate capture theory method for a given class of ion-molecule reaction and set of experimental conditions-identifying when a capture-based model is likely to provide an accurate prediction. Finally, the impact of capture theories on fields such as astrochemical modeling is noted, with some potential future directions of capture-based approaches outlined.
自 Arrhenius 于 1889 年首次提出一个方程来解释热激活反应的行为以来,我们对化学反应性的理解已经取得了重大进展。在过去的几十年中,已经开发出了许多捕获理论模型来预测离子和分子之间反应的速率系数——从 Langevin 方程(用于离子和非极性分子之间的反应)到最近的全量子理论(用于极低温下的反应)。本文讨论了许多不同的捕获理论方法,并清楚地阐述了每种方法的关键假设。通过低温实验测量和捕获理论预测之间的详细比较,研究了这些捕获理论方法的优缺点。为给定的离子-分子反应类别和一组实验条件选择合适的捕获理论方法提供了指导——确定何时基于捕获的模型可能提供准确的预测。最后,还注意到了捕获理论对天体化学建模等领域的影响,并概述了基于捕获的方法的一些潜在未来方向。