Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Japan.
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
J Chem Theory Comput. 2021 Nov 9;17(11):6901-6909. doi: 10.1021/acs.jctc.1c00693. Epub 2021 Oct 25.
The one-to-one correspondence between reaction pathways in the potential energy theory and reactive orbitals in the electronic theory for reactions is presented. In this study, the reactive orbital energy method is applied to the intrinsic reaction coordinates of the global reaction route map generated by an automated reaction path search method. The reactive orbital energy method specifies the pairs of occupied and unoccupied reactive orbitals driving chemical reactions and determines whether the reactions are electron transfer-driven or dynamics-driven. Surprisingly, it is found that the reactive orbital pairs are determined one by one for the electron transfer-driven reaction pathways from an identical molecule. The reactive orbital energy method is also found to provide the sophisticated interpretations of reactions for the electronic motions. This one-to-one correspondence is expected to trigger the unification of the potential energy theory and the electronic theory for reactions that have been independently developed.
呈现了势能理论中的反应途径与电子理论中反应的活性轨道之间的一一对应关系。在这项研究中，活性轨道能量方法被应用于通过自动化反应路径搜索方法生成的全局反应路径图的本征反应坐标。活性轨道能量方法指定了驱动化学反应的占据轨道和非占据轨道对，并确定反应是电子转移驱动还是动力学驱动。令人惊讶的是，发现在相同分子的电子转移驱动反应途径中，活性轨道对是一个一个地确定的。活性轨道能量方法还发现，它为电子运动提供了对反应的复杂解释。这种一一对应有望引发已经独立发展的势能理论和反应电子理论的统一。
