Accessing slow diffusion in solids by employing metadynamics simulation

Molecular dynamics (MD) is a powerful tool to investigate microscopic transport of atoms and molecules in condensed matter. However, there lies a large class of systems wherein atomic diffusion is too slow a process relative to the feasible time scales of typical atomistic simulations. Here, we demonstrate that with judicial implementation of a metadynamics (MTD) technique, the microscopic mechanism of atomic transport in solids can be accessed within a reasonable computational time. The calculations are carried out on the two end members of the true NASICON solid solutions, namely NaZr2(PO4)3 and Na4Zr2(SiO4)3, wherein Na+ diffusion is too slow to be accessed through standard MD simulations. The study also provides fresh insights on correlated ion hops and their implications on the effective diffusion barrier. The results are compared with climbing image nudged elastic band (CI-NEB) calculation, and available experimental results.