Extended Lagrangian molecular dynamics on vibronic surfaces in the nuclear-electronic orbital framework

TL;DR

This paper introduces a novel extended Lagrangian molecular dynamics method within the nuclear-electronic orbital framework, enabling efficient and accurate simulation of proton transfer dynamics including quantum effects.

Contribution

The paper develops the NEO-ELMD approach with density matrix extrapolation to accelerate simulations of proton transfer within the NEO-DFT framework, incorporating nuclear quantum effects.

Findings

Demonstrates fidelity of NEO-ELMD in proton transfer simulations

Achieves computational efficiency through density matrix extrapolation

Successfully simulates large proton-coupled electron transfer systems

Abstract

Proton transfer is central to many processes of chemical interest. The simulation of proton transfer dynamics requires the inclusion of nuclear quantum effects, such as zero-point energy, nuclear delocalization, and tunneling. Herein, we introduce methods within the nuclear-electronic orbital (NEO) framework, where specified nuclei are treated quantum mechanically on the same level as the electrons, for the simulation of proton transfer dynamics. Specifically, NEO density functional theory is used to treat the transferring protons quantum mechanically, and the other nuclei are propagated classically on the adiabatic vibronic ground-state surface. We formulate a NEO extended Lagrangian molecular dynamics (NEO-ELMD) approach to incorporate the motion of the nuclear basis function centers during such simulations. Density matrix extrapolation and purification are introduced as a means to accelerate the NEO self-consistent field procedure at each time step by reducing the number of iterations required for convergence. We demonstrate the fidelity and efficiency of NEO-ELMD by comparison to related dynamics methods for intramolecular proton transfer in malonaldehyde. We also use these accelerated techniques to simulate the nonequilibrium single and double proton transfer dynamics of proton-coupled electron transfer in much larger benzimidazole-phenol systems. This work provides a foundation for future methodologies to efficiently simulate proton transfer dynamics within the NEO-DFT framework while incorporating nonadiabatic effects between adiabatic vibronic states.