The sum over histories representation for chemical kinetics: a quantitative theory based on chemical pathways

IF 2.5 2区 化学 Q3 CHEMISTRY, PHYSICAL
Shirong Bai, R. T. Skodje
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引用次数: 11

Abstract

A new representation for chemical kinetics based on a sum over histories formulation is discussed. The description of the time-dependent chemistry of a reaction network is provided by chemical pathways defined at a molecular level. Using this methodology, the quantitative time evolution of the kinetics is described by enumerating the most important pathways followed by a chemical moiety such as a tagged atom. An explicit formula for the pathway probabilities is derived which takes the form of an integral over a time-ordered product. This expression has a simple and computationally efficient Monte Carlo representation which permits the method to be applied to a wide range of problems. For small reaction networks, the chemical pathways can be enumerated using graph theoretic methods. More complicated networks can be explored using random walks computed from a stochastic algorithm. The workings of the method are illustrated using a simple network of 20 chemical species which react via first-order kinetics. The application of the sum over histories representation to problems in surface catalysis and hydrogen combustion provide more realistic applications.
化学动力学的历史总和表示:一种基于化学途径的定量理论
讨论了化学动力学的一种基于历史和公式的新表示。反应网络的随时间变化的化学描述是由在分子水平上定义的化学途径提供的。使用这种方法,动力学的定量时间演化是通过列举最重要的途径来描述的,随后是一个化学片段,如一个标记的原子。导出了路径概率的显式公式,其形式为时间顺序积上的积分。该表达式具有简单且计算效率高的蒙特卡罗表示,这使得该方法可以应用于广泛的问题。对于小型反应网络,可以用图论方法列举化学途径。更复杂的网络可以使用随机算法计算的随机游走来探索。该方法的工作原理是用20种化学物质通过一级动力学反应的简单网络来说明的。历史和表示法在表面催化和氢燃烧问题中的应用提供了更现实的应用。
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来源期刊
CiteScore
14.20
自引率
1.60%
发文量
5
审稿时长
1 months
期刊介绍: International Reviews in Physical Chemistry publishes review articles describing frontier research areas in physical chemistry. Internationally renowned scientists describe their own research in the wider context of the field. The articles are of interest not only to specialists but also to those wishing to read general and authoritative accounts of recent developments in physical chemistry, chemical physics and theoretical chemistry. The journal appeals to research workers, lecturers and research students alike.
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