Tsutsumi Takuro, Ono Yuriko, Taketsugu Tetsuya
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Japan.
Chem Commun (Camb). 2021 Nov 9;57(89):11734-11750. doi: 10.1039/d1cc04667e.
In the quantum chemical approach, chemical reaction mechanisms are investigated based on a potential energy surface (PES). Automated reaction path search methods enable us to construct a global reaction route map containing multiple reaction paths corresponding to a series of elementary reaction processes. The on-the-fly molecular dynamics (MD) method provides a classical trajectory exploring the full-dimensional PES based on electronic structure calculations. We have developed two reaction analysis methods, the on-the-fly trajectory mapping method and the reaction space projector (ReSPer) method, by introducing a structural similarity to a pair of geometric structures and revealed dynamic aspects affecting chemical reaction mechanisms. In this review, we will present the details of these analysis methods and discuss the dynamics effects of reaction path curvature and reaction path bifurcation with applications to the CHOH + OH collision reaction and the Au cluster branching and isomerization reactions.
在量子化学方法中，基于势能面（PES）研究化学反应机理。自动反应路径搜索方法使我们能够构建一个包含与一系列基元反应过程相对应的多个反应路径的全局反应路线图。实时分子动力学（MD）方法提供了一条基于电子结构计算探索全维势能面的经典轨迹。通过引入一对几何结构的结构相似性，我们开发了两种反应分析方法，即实时轨迹映射方法和反应空间投影器（ReSPer）方法，并揭示了影响化学反应机理的动态方面。在这篇综述中，我们将介绍这些分析方法的细节，并通过应用于CHOH + OH碰撞反应以及金团簇分支和异构化反应，讨论反应路径曲率和反应路径分叉的动力学效应。
Zotero 插件