Geometric Rotation of the Nuclear Gradient at a Conical Intersection: Extension to Complex Rotation of Diabatic States

摘要: Nonadiabatic dynamics in the vicinity of conical intersections is essential importance photochemistry. It well known that if branching space represented polar coordinates, then for a geometry by angle θ, corresponding adiabatic states are obtained from diabatic with mixing θ/2. In an equivalent way, one can study relation between real rotation and resulting nuclear gradient. this work, we extend concept to allow complex form nonstationary superposition electronic states. Our main result leads elliptical transformation effective potential energy surfaces; i.e., magnitude initial gradient changes as its direction. We fully explore varying both θ ϕ (the angle) way electronically controlling motion, through Ehrenfest simulations benzene cation.