title: A new perovskite polytype in the high-pressure sequence of BaIrO(3).
abstract: The high-pressure sequence of the perovskite polytypes of BaIrO(3) has been investigated in the pressure range up to 10 GPa. At ambient pressure the so-called "9R" polytype has been prepared by solid-state reaction and slow cooling in air to yield an almost fully oxygen-stoichiometric BaIrO(2.96(1)) composition. The crystal structure has been refined from XRD data in the monoclinic C2/m space group with a = 10.0046(3) A, b = 5.75362(14) A, c = 15.1839(4) A, beta = 103.27(1) degrees ; it contains trimers of face-sharing octahedra (or Ir(3)O(12) trioctahedra) that are linked by their vertices to form columns parallel to the c-axis with a stacking of layers of corner sharing (c) and face sharing (h) IrO(6) octahedra along the sequence hhchhc. This structure is stable up to 3 GPa; at 4 GPa a new 5H polytype has been stabilized as a pure phase. The crystal structure has been solved by ab initio procedures from powder XRD data. It is monoclinic with a = 9.9511(2) A, b = 5.7503(1) A, c = 13.71003(3) A, beta = 118.404(2) degrees , and it was refined in the C2/m space group from NPD data collected at room temperature. This polytype can be described as a stacking of IrO(6) octahedra along the sequence hchcc. The structure contains chains of double dimer units of face-sharing octahedra; the twin dimers are connected to single layers of vertex-sharing octahedra, forming infinite chains along c. This is a unique stacking that, with this repetition length, has never been described before among the hexagonal polytypes of ABO(3) perovskites. The 5H polytype is stable in a narrow pressure range; at 5 GPa the 6H structure is formed, stable up to 10 GPa. The 6H-BaIrO(3) polytype is monoclinic, space group C2/c, with a = 5.7483(2) A, b = 9.9390(3) A, c = 14.3582(5) A, beta = 91.319(2) degrees . The structure consists of dimers of face-sharing octahedra separated by single corner-sharing octahedra, showing the sequence hcchcc along the c-axis. At 10 GPa the cubic 3C perovskite structure could be identified as a minority phase, with a = 4.0611(7) A, defined in the Pm3m space group. The precarious stability of the 5H polytype, as well as the novel pressure sequence displayed by BaIrO(3) that is distinct from the classical sequence 9R-4H-6H-3C exhibited by many transition metal oxides, for instance BaRuO(3), is a result of the particular stability of the "9R" ambient-pressure structure, which is reinforced by a strong Ir-Ir bond across the octahedral faces, and the Ir-Ir Coulombic repulsion across shared faces that destabilizes the 4H polytype relative to the 6H phase to allow stabilization of the hybrid 5H polytype in a narrow presure range.
authors.affiliation: Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, Texas 78712, USA.
authors.forename: Jin-Guang
authors.initials: JG
authors.lastname: Cheng
authors.forename: José Antonio
authors.initials: JA
authors.lastname: Alonso
authors.forename: Emmanuelle
authors.initials: E
authors.lastname: Suard
authors.forename: Jian-Shi
authors.initials: JS
authors.lastname: Zhou
authors.forename: John B
authors.initials: JB
authors.lastname: Goodenough