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

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.