Stueckelberg Oscillations in a Two‐State Two‐Path Model of a Conical Intersection

Abstract

AbstractThe two‐state two‐path model is introduced as a minimized model to describe the quantum dynamics of an electronic wave packet in the vicinity of a conical intersection. It involves two electronic potential energy surfaces each of which hosts a pair of quasi‐classical trajectories over which the wave packet is assumed to be delocalized. When both trajectories evolve dynamically either diabatically or adiabatically, the full wave packet dynamics shows only features of the dynamics around avoided level crossings in the vicinity of the conical intersection. When one trajectory evolves adiabatically whereas the other trajectory follows a diabatic evolution, quantum mechanical interference of the wave packet components on each path generates Stueckelberg oscillations in the transition probability. These are surprisingly robust against a dissipative environment and, thus, should be a marker for conical intersections.