Superionic UO_{2} crystal: How to model its relaxation and diffusion via a microscopic theory of glass-forming liquids.

Abstract

UO_{2} is a crucial nuclear material but its behaviors are elusive due to the impact of superionic diffusion. Herein, we introduce a simple but effective theoretical model to describe the intrinsic superionicity of UO_{2} at the quantitative level. Our idea stems from a close similarity between superionic crystals and supercooled liquids. Namely, we view UO_{2} as a randomly pinned hard-sphere fluid in the framework of the elastically collective nonlinear Langevin equation theory. This treatment allows us to fully evaluate the contribution of local, collective, pinning, and screening effects to the molecular dynamics of UO_{2} without complex computational processes. Finite-temperature factors are considered via volumetric expansion during isobaric heating. On that basis, we satisfactorily explain recent large-scale atomistic simulations on UO_{2} under various thermodynamic conditions. Our calculations also reveal that UO_{2} is equivalent to an intermediate glass former. Its structural relaxation, self-diffusion, and shear deformation are strongly correlated near the onset of superionicity. These intimate correlations are reminiscent of the famed Dyre shoving model in the soft-matter community. Our results promise to facilitate the development of diverse energy applications of UO_{2}.