Phenomenological Ehrenfest Dynamics with Topological and Geometric Phase Effects and the curious case of Elliptical intersection (2510.14181v1)

Abstract: We present a comprehensive computational framework for simulating nonadiabatic molecular dynamics with explicit inclusion of geometric phase (GP) effects. Our approach is based on a generalized two-level Hamiltonian model that can represent various electronic state crossings - conical intersections, avoided crossings, and elliptic intersections - through appropriate parameterization. We introduce a novel prelooping trajectory initialization scheme, allowing us to encode the memory as an initial phase accumulated due to the adiabatic evolution over the potential energy surface. This is a unified framework to handle different types of level crossings by incorporating Berry curvature-based force corrections to Ehrenfest dynamics, ensuring accurate representation of topological effects. For conical intersections, our method incorporates the theoretically expected phase pi, while for elliptic intersections, it yields a parametrically tunable but loop radius (energy) independent phase different from pi. We also include an eccentricity parameter (e) in the diabatic coupling to model more realistic molecular systems. Numerical simulations demonstrate the consistency of our approach with theoretical predictions for mixing of states and inhibition from mixing due to geometric phase effects. This framework provides a valuable tool for studying quantum-classical interactions in molecular systems where geometric phase effects play a significant role. The elliptical intersection and geometric phase effect opens avenue for the design and discovery of degenerate materials. It produces a fresh look to help develop a new kind of spectroscopy and potential qubit applications. This simple Hamiltonian reveals a pathological phase protection effect E = kr, where k is real, that has great utility in a new spectroscopy design.