Synthesis, Anion Disordering and Electronic Structure of Rb2KWO3F3 Elpasolite

https://doi.org/10.3390/cryst16010018

Rb₂KWO₃F₃ elpasolite was synthesized via the solid-state reaction route. The phase purity of the obtained sample was verified by the XRD analysis with Rietveld refinement in space group Fm-3m, yielding the unit cell parameter a = 8.92413 (17) Å. The electronic structure and chemical states of the constituent elements were investigated using X-ray photoelectron spectroscopy. The binding energy of the W 4f_7/2 core level (34.95 eV) was found to be characteristic of the W⁶⁺ oxidation state, while the values for Rb 3d, K 2p, O 1s and F 1s levels were consistent with those reported for related oxide and oxyfluoride compounds. First-principles density functional theory calculations were performed to model the electronic structure. The fac-configuration of the WO₃F₃ octahedra was identified as the most energetically favorable. The calculations revealed a direct band gap of 4.38 eV, with the valence band maximum composed primarily of O 2p orbitals and the conduction band minimum formed by W 5d orbitals. This combined experimental/theoretical study shows that the electronic structure and wide bandgap of Rb₂KWO₃F₃ are governed by the WO₃F₃ units and are largely insensitive to the Rb/K substitution. The wide bandgap identifies this class of oxyfluorides as a promising platform for developing new UV-transparent materials.