Benchmark Crystal Structure of Defect-Free Spinel ZnFe 2 O 4 .

Accurate structural models are of paramount importance for elucidating structure-property relationships in functional materials. Spinels (ABO) form a highly important family of materials with complex crystal structures, and subtle structural details have a critical bearing on understanding their physical properties. In some spinels, the space group symmetry is debated, and in general, point defects such as cation inversion and interstitials add complexity. Most studies of spinels concern powder materials, and this challenges deep structural characterization. In fact, most published spinel structures have dubious atomic displacement parameters (ADPs), which is a typical sign of problematic structural description in the refinement of diffraction data. Here, we use various X-ray and neutron diffraction techniques to establish a benchmark crystal structure for the essentially defect-free spinel ferrite ZnFeO, which is a widely studied frustrated magnet. It is shown that the appearance of 3̅ forbidden reflections in the ZnFeO single-crystal neutron diffraction data is an artifact of multiple scattering rather than the loss of inversion symmetry. We then provide benchmark ADPs and demonstrate how strongly these parameters affect the refined cation inversion. The ADPs reported here may be used as reference data to test the soundness of refined structural models, possibly to constrain those based on suboptimal data quality, and thereby provide a more accurate fundamental understanding of the structure-property relationship in spinel-type materials.