Modeling Reactions on the Solid–Liquid Interface with Next Generation Extended Lagrangian Quantum-Based Molecular Dynamics

Abstract We present a series of simulations of the oxygen reduction reaction (ORR) using a novel framework for atomistic simulations of surface catalysis under electrochemical bias. The framework makes use of quantum-mechanical extended Lagrangian Born–Oppenheimer molecular dynamics (XL-BOMD) simulations, which provide the speed and accuracy required for explicit atomistic treatment of both electrode and electrolyte. Simulations of solvated O2 near nitrogen-doped graphene (NG) were performed to gain insight into the ORR, and different mechanisms were observed, depending on the applied bias. Under higher bias the ORR occurred by an outer-sphere mechanism, without adsorption of O2 to NG. In this mechanism, electron transfer between the catalyst and the O2 was mediated by the solvent. Under lower bias the ORR occurred by an inner-sphere mechanism involving adsorption of O2 to NG, leading to direct electron transfer. Our extensive, all-atom quantum-mechanical molecular dynamics simulations also show clear differences between the kinetics of the ORR on this ideally polarizable electrode and commonly used kinetic theories, leading to new insights regarding mechanistic changes with varied overpotentials. Combining quantum accuracy with explicit solvation and electrostatic potential bias, XL-BOMD opens a route to predictive, atomistic insight into electrocatalytic processes, as demonstrated with the ORR.