Exploring Exact-Factorization-Based Trajectories for Low-Energy Dynamics near a Conical Intersection.

Abstract

We study low-energy dynamics generated by a two-dimensional two-state Jahn-Teller Hamiltonian in the vicinity of a conical intersection using quantum wave packet and trajectory dynamics. Recently, these dynamics were studied by comparing the adiabatic representation and the exact factorization, with the purpose to highlight the different nature of topological-phase and geometric-phase effects arising in the two theoretical representations of the same problem. Here, we employ the exact factorization to understand how to accurately model low-energy dynamics in the vicinity of a conical intersection using an approximate description of the nuclear motion that uses trajectories. We find that since nonadiabatic effects are weak but non-negligible, the trajectory-based description that invokes the classical approximation struggles to capture the correct behavior.