Ab initio modeling of oxygen impurity atom incorporation into uranium mononitride surface and subsurface vacancies

TL;DR

This study uses ab initio calculations to explore how oxygen atoms incorporate into uranium mononitride surfaces and vacancies, revealing a preference for N-vacancies and insights into oxidation mechanisms.

Contribution

The paper provides detailed computational analysis of oxygen incorporation into UN vacancies, highlighting energetic preferences and electronic structure changes, which were not previously characterized.

Findings

Oxygen prefers N-vacancies over U-vacancies in UN.

Oxygen incorporation stabilizes at N-vacancies, influencing oxidation.

Electronic structure analysis shows charge redistribution around vacancies.

Abstract

The incorporation of oxygen atoms has been simulated into either nitrogen or uranium vacancy at the UN(001) surface, sub-surface or central layers. For calculations on the corresponding slab models both the relativistic pseudopotentials and the method of projector augmented-waves (PAW) as implemented in the VASP computer code have been used. The energies of O atom incorporation and solution within the defective UN surface have been calculated and discussed. For different configurations of oxygen ions at vacancies within the UN(001) slab, the calculated density of states and electronic charge re-distribution was analyzed. Considerable energetic preference of O atom incorporation into the N-vacancy as compared to U-vacancy indicates that the observed oxidation of UN is determined mainly by the interaction of oxygen atoms with the surface and sub-surface N vacancies resulting in their capture by the vacancies and formation of O-U bonds with the nearest uranium atoms. Keywords: Density functional calculations, uranium mononitride, surface, defects, N and U vacancies