Lee Heesung, Kim So-Yeon, Kim Sang Kyu
Department of Chemistry , KAIST , Daejeon 34141 , Republic of Korea . Email:
Chem Sci. 2020 Jun 16;11(26):6856-6861. doi: 10.1039/d0sc02045a. eCollection 2020 Jul 14.
Multidimensional conical intersection seam has been characterized by utilizing the dynamic resonances in the nonadiabatic transition probability experimentally observed in the predissociation of thioanisole isotopomers. The nonadiabatic bifurcation behavior of the reactive flux into either the Herzberg type-I (electronic) or type-II (vibrational) predissociation pathway is found to be strongly dependent on the quantum nature of the S/S vibronic eigenstate, providing the essential information about structure and dynamic character of the conical intersection seam projected onto the normal mode space. By modifying the nature of the normal mode space through partial or full H/D substitution of the molecule, multiple aspects of the conical intersection seam could be characterized from different viewpoints set by the adjusted normal mode space. Theoretical calculations of potential energy curves along selected normal mode displacements support the experiment.
通过利用在硫代苯同位素异构体预解离实验中观察到的非绝热跃迁概率中的动态共振，对多维锥形交叉缝进行了表征。发现反应通量进入赫兹伯格I型（电子）或II型（振动）预解离途径的非绝热分支行为强烈依赖于S/S振转本征态的量子性质，这提供了关于投影到简正模式空间上的锥形交叉缝的结构和动态特征的基本信息。通过对分子进行部分或完全的H/D取代来改变简正模式空间的性质，可以从由调整后的简正模式空间设定的不同视角来表征锥形交叉缝的多个方面。沿选定简正模式位移的势能曲线的理论计算支持了该实验。
