Modeling the Kinetics of Bimolecular Reactions
Modeling the Kinetics of Bimolecular Reactions
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DOI：
10.1002/chin.200703270
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发表时间：
2007-01
期刊：
影响因子：
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通讯作者：
A. Fernández-Ramos;James A. Miller;S. Klippenstein;D. Truhlar
中科院分区：
文献类型：
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作者：
A. Fernández-Ramos;James A. Miller;S. Klippenstein;D. Truhlar
本综述涉及双分子反应的理论和计算模型，特别是动力学的一般适用方法（即，总体速率而不是详细动力学）。它包括一个基本的理论框架，可以用于气相热反应，气相微规范和状态选择反应，以及冷凝相化学反应。气相热反应的处理包括单独讨论在势垒上的简单直接反应，这些反应通常具有紧密的过渡态，而在化学势井上进行的反应可能具有许多额外的复杂性，例如无势垒加成势（通常具有松散、灵活的过渡态）、竞争反应途径、多井之间的异构化以及依赖于压力的能量传递过程。热反应部分着重强调（广义）过渡态理论（TST），包括多维隧道效应，因为该理论提供了除最简单系统外所有系统的热速率常数计算的最佳方法。关于状态选择反应和产物状态分布的部分包括介绍电子非绝热反应和耦合势能面理论，这是模拟光化学和化学发光反应所必需的。液体溶液中的双分子反应部分考虑了扩散控制、平衡和非平衡溶剂化。
This review is concerned with the theoretical and computational modeling of bimolecular reactions, especially with generally applicable methods for kinetics (ie, overall rates as opposed to detailed dynamics). It includes a basic theoretical framework that can be used for gas-phase thermal reactions, gas-phase microcanonical and state-selected reactions, and condensed-phase chemical reactions. The treatment of gas-phase thermal reactions includes separate discussions of simple direct reactions over a barrier, which usually have tight transition states and reactions proceeding over a chemical potential well, which can have a number of additional complications, such as barrierless addition potentials (which generally have loose, flexible transition states), competitive reaction pathways, isomerizations between multiple wells, and pressure-dependent energy transfer processes. The section on thermal reactions has a heavy emphasis on (generalized) transition state theory (TST) including multidimensional tunneling because this theory provides the best available method to calculate thermal rate constants for all but the very simplest systems. The section on state-selective reactions and product state distributions includes an introduction to the theory of electronically nonadiabatic reactions and coupled potential energy surfaces, as required for modeling photochemical and chemiluminescent reactions. The section on bimolecular reactions in liquid solution considers diffusion control and equilibrium and nonequilibrium solvation.