Evidence for percolation diffusion of cations and reordering in disordered pyrochlore from accelerated molecular dynamics.

Abstract

Diffusion in complex oxides is critical to ionic transport, radiation damage evolution, sintering, and aging. In complex oxides such as pyrochlores, anionic diffusion is dramatically affected by cation disorder. However, little is known about how disorder influences cation transport. Here, we report results from classical and accelerated molecular dynamics simulations of vacancy-mediated cation diffusion in Gd₂Ti₂O₇ pyrochlore, on the microsecond timescale. We find that diffusion is slow at low levels of disorder, while higher disorder allows for fast diffusion, which is then accompanied by antisite annihilation and reordering, and thus a slowing of cation transport. Cation diffusivity is therefore not constant, but decreases as the material reorders. We also show that fast cation diffusion is triggered by the formation of a percolation network of antisites. This is in contrast with observations from other complex oxides and disordered media models, suggesting a fundamentally different relation between disorder and mass transport.Diffusion plays an important role in sintering, damage tolerance and transport. Here authors perform classical and accelerated molecular dynamics simulations of vacancy-mediated cation diffusion in Gd₂Ti₂O₇ pyrochlore and report non-monotonic evolution of cation diffusivity.