The Sluggish Diffusion of Cations in CeO2 Probed through Molecular Dynamics and Metadynamics Simulations

S K├Ârfer and A Bonkowski and J Kler and P Hatton and BP Uberuaga and RA De Souza, ADVANCED ENGINEERING MATERIALS, 25 (2023).

DOI: 10.1002/adem.202201788

Cation diffusion in fluorite-structured CeO2, though far slower than anion diffusion, is an important, high-temperature process because it governs diverse fabrication and degradation phenomena. Herein, cation diffusion is studied by means of classical molecular dynamics and metadynamics simulations. Three different mechanisms are examined: migration involving an isolated cerium vacancy, migration involving a cerium vacancy in a defect associate with an oxygen vacancy, and migration involving a cation divacancy. For each mechanism, defect diffusion coefficients are calculated as a function of temperature, from which the respective activation enthalpy of defect migration is obtained. Through comparisons with experimental cation diffusion data (specifically, of the absolute magnitude of the cation diffusivity as well as its activation enthalpy), it is concluded that cation diffusion takes place predominantly neither by isolated vacancies nor by cation vacancy-oxygen vacancy associates but by cation divacancies.

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