Half Antiperovskites: IV. Crystallographic and Electronic Structure Investigations onA2Rh3S2(A= In, Sn, Tl, Pb, Bi)

Abstract

AbstractThe crystal and electronic structures of ordered half antiperovskitesA2Rh3S2=ARh3/2S (A= In, Sn, Tl, Pb, Bi) are investigated. From powder and single crystal data superstructures, rhodium site ordering, trends in bonding and coordination are analysed with respect to theAsite atom. Comparisons address isotypic and isoelectronic relations to monoclinic parkerite (Bi2Ni3S2) type superconductors, the trigonal half‐metal ferromagnet Sn2Co3S2, and rhodium‐containing antiperovskites. Local structure and bonding is analysed with respect to the ordered occupation of half of S2A4sites (= perovskite oxygen sites) and interlinking to 2D networks [Rh3S2]∞δ–by face‐, edge‐ and corner‐sharing. The theoretical part includes DFT band structure and ELF calculations, systematic comparisons to rhodium and antiperovskites, as well as spin‐polarised calculations on Sn2Rh3S2and Pb2Rh3S2.