Nonadiabatic Dynamics with Constrained Nuclear-Electronic Orbital Theory

Abstract

Incorporating nuclear quantum effects into nonadiabatic dynamics remains a significant challenge. Herein we introduce new nonadiabatic dynamics approaches based on the recently developed constrained nuclear-electronic orbital (CNEO) theory. The CNEO approach integrates nuclear quantum effects, particularly quantum nuclear delocalization effects, into effective potential energy surfaces. When combined with Ehrenfest dynamics and surface hopping, it effectively captures both nonadiabaticity and quantum nuclear delocalization effects. We apply these new approaches to a one-dimensional proton-coupled electron transfer model and find that they outperform conventional Ehrenfest dynamics and surface hopping, particularly in accurately predicting proton transfer dynamics and proton transmission probabilities in the low-momentum regime.