Large Positive Thermal Expansion and Small Band Gap in Double-ReO₃-Type Compound NaSbF₆

Double-ReO₃-type structure compound NaSbF₆ undergoes a low-temperature rhombohedral to high-temperature cubic phase between 303 and 323 K, as revealed by temperature-dependent X-ray diffractions. Although many double-ReO₃-type fluorides exhibit either low thermal expansion or negative thermal expansion (NTE), NaSbF₆ exhibits positive thermal expansion (PTE) with a large volumetric coefficient of thermal expansion, α_v = 62 ppm/K, in its cubic phase. Raman spectroscopy reveals that the low-frequency transverse vibration of fluorine atoms is stiffened in NaSbF₆, compared with the typical NTE compound CaZrF₆ with the same structure. The related weak contraction associated with the polyhedral rocking would be overcome by the notable elongation of the Na-F bond length on heating, thus leading to the large volumetric PTE. Unlike ScF₃ and CaZrF₆ which are insulators with a wide band gap, a relative small band gap of 3.76 eV was observed in NaSbF₆. The small band gap can be attributed to the hybridization between the Sb 5s and F 2p orbitals.