Multi-state Energy Landscape for Photoreaction of Stilbene and Dimethyl-stilbene
Multi-state Energy Landscape for Photoreaction of Stilbene and Dimethyl-stilbene
复制标题
二苯乙烯和二甲基二苯乙烯光反应的多态能量景观
DOI：
10.1021/acs.jctc.2c00560
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发表时间：
2022
影响因子：
5.5
通讯作者：
Taketsugu Tetsuya
中科院分区：
文献类型：
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作者：
Tsutsumi Takuro;Ono Yuriko;Taketsugu Tetsuya
我们最近开发了反应空间投影（ReSPer）方法，该方法构造了一个降维的反应空间，该反应空间由多原子分子系统的参考反应路径唯一确定，并将经典轨迹投影到同一反应空间中。在本文中，我们扩展ReSPer的光反应动力学和弛豫过程的分析芪和提出的概念，“多状态的能量景观”，将地面和激发态反应子空间。多态能量图景成功地解释了先前建立的顺式二苯乙烯的光化学反应过程，如顺式光转异构化和光环化。此外，基于不同原子数的参比结构的骨架部分确定的共同反应子空间，讨论了二苯乙烯和1，1 ′-二甲基二苯乙烯在激发态反应动力学上的差异.这种方法使我们能够靶向具有共同框架的任何分子，大大扩展了ReSPer分析的适用性。多状态能量景观提供了富有成效的洞察光化学反应，探索激发态和基态势能面，以及全面的反应过程与绝热状态之间的非辐射跃迁，在一个降维反应空间的阶段。
We have recently developed the reaction space projector (ReSPer) method, which constructs a reduced-dimensionality reaction space uniquely determined from reference reaction paths for a polyatomic molecular system and projects classical trajectories into the same reaction space. In this paper, we extend ReSPer to the analysis of photoreaction dynamics and relaxation processes of stilbene and present the concept of a “multi-state energy landscape,” incorporating the ground- and excited-state reaction subspaces. The multi-state energy landscape successfully explains the previously established photoreaction processes ofcis-stilbene, such as thecis–transphotoisomerization and photocyclization. In addition, we discuss the difference in the excited-state reaction dynamics between stilbene and 1,1′-dimethyl stilbene based on a common reaction subspace determined from the framework part of reference structures with different number of atoms. This approach allows us to target any molecule with a common framework, greatly expanding the applicability of the ReSPer analysis. The multi-state energy landscape provides fruitful insight into photochemical reactions, exploring the excited- and ground-state potential energy surfaces, as well as comprehensive reaction processes with nonradiative transitions between adiabatic states, within the stage of a reduced-dimensionality reaction space.