Xenon-metal pair formation in UO₂ investigated using DFT + U

A recent experimental study on a spent uranium dioxide (UO₂) fuel sample from Belgium Reactor 3 identified a unique pair structure formed by the noble metal phase (NMP) and fission gas [xenon (Xe)] precipitate. However, the fundamental mechanism behind this structure remains unclear. The present study aims to provide an understanding of the interaction between five different metal precipitates [molybdenum (Mo), ruthenium (Ru), palladium (Pd), technetium (Tc), and rhodium (Rh)] and the Xe fission gas atoms in UO₂, by using density functional theory (DFT) in combination with the Hubbard U correction to compute the formation energies involved. All DFT + U calculations were performed with occupation matrix control to ensure antiferromagnetic ordering of UO₂. The calculated formation and binding energies of the Xe and solid fission products in the NMP reveal that these metal precipitates form stable pair structures with Xe. Notably, the formation energy of Xe-metal pairs is lower than that of the isolated single defects in all instances, with Pd and Mo showing the most favorable binding energy, likely accounting for the observed pair structure formation.