Nonadiabatic Dynamics with Constrained Nuclear-Electronic Orbital Theory

Zhe Liu; Zehua Chen; Yang Yang

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arXiv · 2504.08900

Nonadiabatic Dynamics with Constrained Nuclear-Electronic Orbital Theory

Zhe Liu·Zehua Chen·Yang Yang

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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 efficiently 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 in predicting proton transfer dynamics and proton transmission probabilities, especially in the low momentum regime.

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Zhe Liu, Zehua Chen, Yang Yang. 2025-04-11. Nonadiabatic Dynamics with Constrained Nuclear-Electronic Orbital Theory. https://arxiv.org/abs/2504.08900

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