Anomalous Ionic Conductivity along the Coherent $Σ$3 Grain Boundary in ThO2 (2507.04652v1)

Abstract: Understanding oxygen diffusion along grain boundaries (GBs) is critical for controlling ionic conductivity in oxide ceramics. GBs are typically thought to enhance ionic transport due to structural disorder and increased free volume. In this study, we report an unexpected anomaly: the $\Sigma 3(111)$ GB in thorium dioxide (ThO$_2$), despite its compact and coherent structure, exhibits significantly higher oxygen ionic conductivity compared to the more open GB ($\Sigma 19$ as an example). Using atomistic simulations based on a machine learning interatomic potential, we revealed that the high conductivity in the $\Sigma 3$ GB arises from a collective diffusion mechanism involving highly correlated atomic motion reminiscent of a superionic state. In contrast, the $\Sigma 19$ GB follows conventional pipe diffusion, consistent with its more open structure. This comparison highlights that enhanced GB conductivity is not simply correlated with free volume, but can occur from specific structural motifs that enable collective transport. These findings provide new guidance for designing GB-engineered oxides with targeted ionic transport properties for energy applications.