First principles investigations of electronic, magnetic and bonding peculiarities of uranium nitride-fluoride UNF

TL;DR

This study uses density functional theory to explore the unique electronic, magnetic, and bonding properties of uranium nitride fluoride UNF, revealing its layered structure, mixed bonding character, and antiferromagnetic insulating ground state.

Contribution

It provides the first detailed theoretical analysis of UNF's peculiar properties, highlighting its layered structure and mixed covalent-ionic bonding nature.

Findings

UNF has a layered tetragonal structure with mixed anionic sublattices.

U-N bonds are stronger and more covalent than N-F bonds.

UNF is an insulating antiferromagnet with ~2 eV band gap.

Abstract

Based on geometry optimization and magnetic structure investigations within density functional theory, unique uranium nitride fluoride UNF, isoelectronic with UO2, is shown to present peculiar differentiated physical properties. Such specificities versus the oxide are related with the mixed anionic sublattices and the layered-like tetragonal structure characterized by covalent like [U2N2]2+motifs interlayered by ionic like [F2]2- ones and illustrated herein with electron localization function graphs. Particularly the ionocovalent chemical picture shows, based on overlap population analyses, stronger U-N bonding versus N-F and d(U-N) < d(U-F) distances. Based on LDA+U calculations the ground state magnetic structure is insulating antiferromagnet with 2 Bohr Magnetons magnetization per magnetic subcell and ~2 eV band gap.