An Exact Factorization Perspective on Quantum Interferences in Nonadiabatic Dynamics

TL;DR

This paper investigates how nonadiabatic quantum interferences are represented within the exact factorization framework, revealing complex potential energy surface features and their impact on nuclear dynamics in a solvable model.

Contribution

It provides a detailed analysis of the shape of the exact potential energy surface during quantum interferences, highlighting differences from simple crossing cases and showing classical trajectories' behavior.

Findings

Complex features develop in the potential energy surface during strong interferences.

Classical trajectories on the exact surface can approximate nuclear probability distributions.

Quantum interferences significantly alter the shape of the time-dependent potential energy surface.

Abstract

Nonadiabatic quantum interferences emerge whenever nuclear wavefunctions in different electronic states meet and interact in a nonadiabatic region. In this work, we analyze how nonadiabatic quantum interferences translate in the context of the exact factorization of the molecular wavefunction. In particular, we focus our attention on the shape of the time-dependent potential energy surface - the exact surface on which the nuclear dynamics takes place. We use a one-dimensional exactly-solvable model to reproduce different conditions for quantum interferences, whose characteristic features already appear in one-dimension. The time-dependent potential energy surface develops complex features when strong interferences are present, in clear contrast to the observed behavior in simple nonadiabatic crossing cases. Nevertheless, independent classical trajectories propagated on the exact time-dependent potential energy surface reasonably conserve a distribution in configuration space that mimics the one of the exact nuclear probability density.