Multi-Hill Strategy in Metadynamics for Interstitial Diffusion in Crystals

Abstract

We propose an efficient and general strategy of metadynamics (MetaD) for investigating interstitial diffusion in a crystal by exploiting crystallographic symmetry. Assuming complete ignorance of the diffusion phenomenon of interest, the three-dimensional coordinates of the interstitial atom with the periodic boundaries are chosen as the collective variables (CVs). Multiple potential hills are simultaneously deposited at all crystallographically-equivalent positions on the free energy surface (FES) defined in the CV space. As a result, the proposed multi-hill strategy highly accelerates atomic jumps in comparison with the single-hill strategy in the conventional MetaD. The key features are that the FES estimated from the final bias potential is exactly satisfied with the symmetry of the host crystal and that all elementary processes of interstitial diffusion are obtained by the single MetaD simulation without any prior knowledge on the diffusion mechanism. The high efficiency and efficacy of the multi-hill strategy are demonstrated, taking the proton diffusion in barium zirconate with the cubic perovskite structure as a model case.