Geometric Rotation of the Nuclear Gradient at a Conical Intersection: Extension to Complex Rotation of Diabatic States
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- 作者：Jan Meisner ; Morgane Vacher ; Michael J. Bearpark ; Michael A. Robb
- 刊名：Journal of Chemical Theory and Computation
- 出版年：2015
- 出版时间：July 14, 2015
- 年：2015
- 卷：11
- 期：7
- 页码：3115-3122
- 全文大小：519K
- ISSN：1549-9626
文摘
Nonadiabatic dynamics in the vicinity of conical intersections is of essential importance in photochemistry. It is well known that if the branching space is represented in polar coordinates, then for a geometry represented by angle 胃, the corresponding adiabatic states are obtained from the diabatic states with the mixing angle 胃/2. In an equivalent way, one can study the relation between the real rotation of diabatic states and the resulting nuclear gradient. In this work, we extend the concept to allow a complex rotation of diabatic states to form a nonstationary superposition of electronic states. Our main result is that this leads to an elliptical transformation of the effective potential energy surfaces; i.e., the magnitude of the initial nuclear gradient changes as well as its direction. We fully explore gradient changes that result from varying both 胃 and 蠒 (the complex rotation angle) as a way of electronically controlling nuclear motion, through Ehrenfest dynamics simulations for benzene cation.