The Reaction path in chemistry : current approaches and perspectives
The Reaction path in chemistry : current approaches and perspectives
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DOI：
10.1007/978-94-015-8539-2
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发表时间：
1995
期刊：
影响因子：
--
通讯作者：
D. Heidrich
中科院分区：
文献类型：
--
作者：
D. Heidrich
相对于势能或吉布斯能（“自由焓”）的所谓反应路径（RP）是化学中最基本的概念之一。它有助于显示和可视化形成化学反应的复杂微观过程的结果。这个概念是传统过渡态理论（TST）的一个隐含组成部分。反应路径模型和TST形成了一个定性的框架，为化学家提供了更好的理解化学反应和激发他们的想象力。然而，当RP被用作详细探索反应机制的工具时，特别是当它被用作TST以上和以外的反应速率理论的基础时，RP及其邻域的精确计算变得重要。RP是一种理论工具，现在形成了“直接动力学”的“理论心脏”。它对于解释常见化学体系中的反应特别有用。势能面RP的适当定义是必要的，以确保基于它的反应理论将具有足够高的质量。因此，我们必须考虑三个重要的研究领域：-势能面的分析和RP的定义和最佳计算，或者至少是一些选定的和化学上有趣的点。利用RP概念进一步发展了适用于一般化学体系的、超越TST的反应理论的具体版本。
The so-called reaction path (RP) with respect to the potential energy or the Gibbs energy (" free enthalpy") is one of the most fundamental concepts in chemistry. It significantly helps to display and visualize the results of the complex microscopic processes forming a chemical reaction. This concept is an implicit component of conventional transition state theory (TST). The model of the reaction path and the TST form a qualitative framework which provides chemists with a better understanding of chemical reactions and stirs their imagination. However, an exact calculation of the RP and its neighbourhood becomes important when the RP is used as a tool for a detailed exploring of reaction mechanisms and particularly when it is used as a basis for reaction rate theories above and beyond TST. The RP is a theoretical instrument that now forms the" theoretical heart" of" direct dynamics". It is particularly useful for the interpretation of reactions in common chemical systems. A suitable definition of the RP of potential energy surfaces is necessary to ensure that the reaction theories based on it will possess sufficiently high quality. Thus, we have to consider three important fields of research:-Analysis of potential energy surfaces and the definition and best calculation of the RPs or-at least-of a number of selected and chemically interesting points on it.-The further development of concrete vers ions of reaction theory beyond TST which are applicable for common chemical systems using the RP concept.