Long-range proton and hydroxide ion transfer dynamics at the water/CeO2 interface in the nanosecond regime: reactive molecular dynamics simulations and kinetic analysis

Abstract

The structural properties, dynamical behaviors, and ion transport phenomena at the interface between water and cerium oxide are investigated by reactive molecular dynamics (MD) simulations employing neural network potentials (NNPs). The NNPs are trained to reproduce density functional theory (DFT) results, and DFT-based MD (DFT-MD) simulations with enhanced sampling techniques and refinement schemes are employed to efficiently and systematically acquire training data that include diverse hydrogen-bonding configurations caused by proton hopping events. The water interfaces with two low-index surfaces of (111) and (110) are explored with these NNPs, and the structure and long-range proton and hydroxide ion transfer dynamics are examined with unprecedented system sizes and long simulation times. Various types of proton hopping events at the interface are categorized and analyzed in detail. Furthermore, in order to decipher the proton and hydroxide ion transport phenomena along the surface, a counting analysis based on the semi-Markov process is formulated and applied to the MD trajectories to obtain reaction rates by considering the transport as stochastic jump processes. Through this model, the coupling between hopping events, vibrational motions, and hydrogen bond networks at the interface are quantitatively examined, and the high activity and ion transport phenomena at the water/CeO₂ interface are unequivocally revealed in the nanosecond regime.