Lagrangian formulation of nuclear–electronic orbital Ehrenfest dynamics with real-time TDDFT for extended periodic systems

We present a Lagrangian-based implementation of Ehrenfest dynamics with nuclear–electronic orbital (NEO) theory and real-time time dependent density functional theory for extended periodic systems. In addition to a quantum dynamical treatment of electrons and selected protons, this approach allows for the classical movement of all other nuclei to be taken into account in simulations of condensed matter systems. Furthermore, we introduce a Lagrangian formulation for the traveling proton basis approach and propose new schemes to enhance its application for extended periodic systems. Validation and proof-of-principle applications are performed on electronically excited proton transfer in the o-hydroxybenzaldehyde molecule with explicit solvating water molecules. These simulations demonstrate the importance of solvation dynamics and a quantum treatment of transferring protons. This work broadens the applicability of the NEO Ehrenfest dynamics approach for studying complex heterogeneous systems in the condensed phase.

Xu, J.; Zhou, R.; Li. T. E.; Hammes-Schiffer, S.; Kanai, Y. Lagrangian Formulation of Nuclear-Electronic Orbital Ehrenfest Dynamics with Real-time TDDFT for Extended Periodic Systems. J. Chem. Phys., 2024, 161, 194109. https://doi.org/10.1063/5.0230570