Stability of Rare-Earth Oxychloride Phases: Bond Valence Study

Abstract The crystal structures of the tetragonal rare earth ( RE ) oxychlorides, RE OCl ( RE =La–Nd, Sm–Ho, and Y) were studied by X-ray powder diffraction measurements, Rietveld analyses, and bond valence calculations. The tetragonal structure (space group P 4/ nmm , No. 129, Z =2) is stable for all but Er–Lu oxychlorides, which possess a hexagonal structure. The tetragonal structure consists of alternating layers of ( RE O) n n + complex cations and X n − anions, where the rare earth is coordinated to four oxygens and four plus one chlorines in a monocapped tetragonal antiprism arrangement. The Rietveld analyses yielded a coherent series of structural parameters. Preferred orientation an…