The environmental dependence of redox energetics of PuO2 and \alpha-Pu2O3: A quantitative solution from DFT+U calculations

Abstract

We report a comprehensive density functional theory (DFT) + $U$ study of the energetics of charged and neutral oxygen defects in both PuO$_{2}$ and $\alpha$-Pu$_{2}$O$_{3}$, and present a quantitative determination of the equilibrium compositions of reduced PuO$_{2}$ (PuO$_{2-x}$) as functions of environmental temperature and partial pressure of oxygen, which shows fairly agreement with corresponding high-temperature experiments. Under ambient conditions, the endothermic reduction of PuO$_{2}$ to $\alpha$-Pu$_{2}$O$_{3} $ is found to be facilitated by accompanying volume expansion of PuO$_{2-x}$ and the possible migration of O-vacancy, whereas further reduction of $\alpha $-Pu$_{2}$O$_{3}$ is predicted to be much more difficult. In contrast to the endothermic oxidation of PuO$_{2}$,\ the oxidation of $\alpha$-Pu$_{2} $O$_{3}$ is a stable exothermic process.