DFT and two-dimensional correlation analysis methods for evaluating the Pu3+–Pu4+ electronic transition of plutonium-doped zircon.

Understanding how plutonium (Pu) doping affects the crystalline zircon structure is very important for risk management. However, so far, there have been only a very limited number of reports of the quantitative simulation of the effects of the Pu charge and concentration on the phase transition. In this study, we used density functional theory (DFT), virtual crystal approximation (VCA), and two-dimensional correlation analysis (2D-CA) techniques to calculate the origins of the structural and electronic transitions of Zr 1− c Pu c SiO 4 over a wide range of Pu doping concentrations ( c = 0–10 mol%). The calculations indicated that the low-angular-momentum Pu-f xy -shell electron excites an inner-shell O-2s 2 orbital to create an oxygen defect (V O-s ) below c = 2.8 mol%. This oxygen defect then captures a low-angular-momentum Zr-5p 6 5s 2 electron to form an sp hybrid orbital, which exhibits a stable phase structure. When c > 2.8 mol%, each accumulated V O-p defect captures a high-angular-momentum Zr-4d z electron and two Si-p z electrons to create delocalized Si 4+ → Si 2+ charge disproportionation. Therefore, we suggest that the optimal amount of Pu cannot exceed 7.5 mol% because of the formation of a mixture of ZrO 8 polyhedral and SiO 4 tetrahedral phases with the orientation (10-1). This study offers new perspective on the development of highly stable zircon-based solid solution materials. [ABSTRACT FROM AUTHOR]