We demonstrate the applicability of extended Lagrangian Born-Oppenheimer quantum-based molecular dynamics (XL-BOMD) to model electron transfer reactions occurring on solid-liquid interfaces. Specifically, we consider the reduction of O2 as catalyzed at the interface of an N-doped graphene sheet and H2O at fuel cell cathodes. This system is a good testbed for next-generation computational chemistry methods since the electrochemical functionalities strongly depend on atomic-scale quantum mechanics. As opposed to prior iterations of first principles molecular dynamics, XL-BOMD only requires a full self-consistent-charge relaxation during the initial time step. The electronic ground state and total energy are stabilized thereafter through nuclear and electronic equations of motion assisted by an inner-product kernel updated with low-rank approximations. A species charge analysis reveals that the kernel-based XL-BOMD simulation can capture an electron transfer between the PGM-free catalyst and a solvated O2 molecule mediated by H2O, which results in the molecular dissociation of O2.
@article{arxiv.1907.06721,
title = {Modeling solid-liquid interface reactions with next generation extended Lagrangian quantum-based molecular dynamics},
author = {Kevin G. Kleiner and Aparna Nair-Kanneganti and Christian F. A. Negre and Ivana Matanovic and Anders M. N. Niklasson},
journal= {arXiv preprint arXiv:1907.06721},
year = {2020}
}