Charge Localization and Magnetic Correlations in the Refined Structure of UO.

Atomic arrangements in the mixed-valence oxide UO are refined from high-resolution neutron scattering data. The crystallographic model describes a long-range structural order in a UO primitive cell (space group 4/) containing distorted cuboctahedral oxygen clusters. By combining experimental data and electronic structure calculations accounting for spin-orbit interactions, we provide robust evidence of an interplay between charge localization and the magnetic moments carried by the uranium atoms. The calculations predict UO to be a semiconducting solid with a band gap of close to 0.32 eV, and a more pronounced charge-transfer insulator behavior as compared to the well-known Mott insulator UO. Most uranium ions (56 out of 60) occur in 9-fold and 10-fold coordinated environments, surrounding the oxygen clusters, and have a tetravalent (24 out of 60) or pentavalent (32 out of 60) state. The remaining uranium ions (4 out of 60) are not contiguous to the oxygen cuboctahedra and have a very compact, 8-fold coordinated environment with two short (2 × 1.93(3) Å) "oxo-type" bonds. The higher Hirshfeld charge and the diamagnetic character point to a hexavalent state for these four uranium ions. Hence, the valence state distribution corresponds to 24/60 × U(IV) + 32/60 U(V) + 4/60 U(VI). The tetravalent and pentavalent uranium ions are predicted to carry noncollinear magnetic moments (with amplitudes of 1.6 and 0.8 μ, respectively), resulting in canted ferromagnetic order in characteristic layers within the overall fluorite-related structure.