One-to-One Correspondence between Reaction Pathways and Reactive Orbitals.
One-to-One Correspondence between Reaction Pathways and Reactive Orbitals.
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反应路径和反应轨道之间的一一对应。
DOI：
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发表时间：
2021
影响因子：
5.5
通讯作者：
T. Tsuneda
中科院分区：
文献类型：
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作者：
M. Hasebe;Takuro Tsutsumi;T. Taketsugu;T. Tsuneda
给出了势能理论中的反应路径与反应电子理论中的反应轨道之间的一一对应关系。在这项研究中，反应轨道能量方法被应用到由自动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中。反应轨道能量法规定了驱动化学反应的占据和未占据的反应轨道对，并确定反应是电子转移驱动的还是动力学驱动的。令人惊讶的是，发现同一分子的电子转移驱动反应路径的反应轨道对是逐个确定的。反应轨道能方法也被发现为电子运动提供了对反应的复杂解释。这种一对一的对应有望触发已独立发展的反应的势能理论和电子理论的统一。
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.