Electronic Coherences in Molecules: The Projected Nuclear Quantum Momentum as a Hidden Agent

Abstract

Electronic coherences are key to understanding and controlling photo-induced molecular transformations. We identify a crucial quantum-mechanical feature of electron-nuclear correlation, the projected nuclear quantum momenta, essential to capture the correct coherence behavior. In simulations, we show that, unlike traditional trajectory-based schemes, exact-factorization-based methods approximate these correlation terms, and correctly capture electronic coherences in a range of situations, including their spatial dependence, an important aspect that influences subsequent electron dynamics and that is becoming accessible in more experiments.