Molecular Dynamics Simulation of Oxygen Diffusion in (PuxTh1-x)O2 Crystals

DD Seitov and KA Nekrasov and DA Ustiuzhanin and AS Boyarchenkov and YA Kuznetsova and SS Pitskhelaury and SK Gupta, CRYSTALS, 15, 919 (2025).

DOI: 10.3390/cryst15110919

Oxygen diffusion in (PuxTh1-x)O2 mixed oxide crystals was investigated using molecular dynamics simulation. The model systems were isolated nanocrystals of 5460 and 15,960 particles, featuring a free surface. The oxygen diffusion coefficient D increased with decreasing thorium content, in accordance with the decrease in the melting temperature of (PuxTh1-x)O2 as x varied from 0 to 1. The temperature dependences D(T) exhibited non-linearity in the Arrhenius coordinates lnD = f(1/kT). The three linear segments of the plots corresponded to the superionic state, a transitional region, and the low-temperature crystalline phase. The transitional region was characterized by maximum values of the effective diffusion activation energy ED(PuO2) = 3.47 eV, ED(ThO2) = 5.24 eV and a complex collective mechanism of oxygen migration, which involved the displacement of anions into interstitial sites. At lower temperatures, an interstitialcy mechanism of oxygen diffusion was observed. The temperature dependence of D(PuO2) showed quantitative agreement with low-temperature experimental data.

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