An Introduction to the Nomenclature and Usage of the Reaction Path Concept
An Introduction to the Nomenclature and Usage of the Reaction Path Concept
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反应路径概念的命名和用法介绍
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发表时间：
1995
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通讯作者：
D. Heidrich
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作者：
D. Heidrich
我们对化学反应的思考极大地受益于作为所谓“反应坐标”（RC）函数的能量分布模型。在教科书中，此类概况通常用于根据过渡态理论 (TST) [1] 来说明化学反应的主要特征，包括其机制。 P.G.Mezey [2] 在他的著作《势能超表面》（第 86 页）中正确地将术语“反应坐标”(RC) 描述为描述反应路径 (RP) 的误导性术语。 “坐标”一词引起了混淆，它表明只有一个主要的内坐标描述了反应路径。在高维系统中使用一个选定的“特异”坐标（或“前导”坐标）（通过在特异坐标的固定值处最小化其他独立内坐标）通常不会产生通过唯一对应于最小能量路径（MEP）的 PES（势能超曲面）的横截面，请参见下文。化学家必须 — nolens volens — 了解高维坐标空间中的一条曲线作为 RP 的实际含义（参见图 1 中的 RC）！将 RP 与 Wilson 的 FG 矩阵 [3] 方法得出的正常模式进行比较可能会有所帮助。
Our thinking about chemical reactions has benefitted greatly from the model of energy profiles as functions of so-called “reaction coordinates” (RC) . In textbooks, such profiles are often used to illustrate the main features of a chemical reaction, including its mechanism, in terms of transition state theory (TST) [1]. In his book “Potential Energy Hypersurfaces” (p. 86), P.G.Mezey [2] rightly describes the term “reaction coordinate” (RC) as a misleading one to characterize the reaction path (RP) . Confusion results from the term “coordinate” which suggests that only one dominant internal coordinate describes the reaction path. The use of one selected “distinguished” coordinate (or “leading” coordinate) in higher-dimensional systems (by minimizing the other independent internal coordinates at fixed values of the distinguished coordinate) generally does not produce cross-sections through a PES (potential energy hypersurface) that uniquely correspond to minimum energy paths (MEP), see below. The chemist must — nolens volens — understand what a curve in the high-dimensional coordinate space taken as RP actually means (cf. RC in Figure 1) ! The comparison of the RP to a normal mode resulting from Wilson’s FG matrix [3] method may be helpful.