B1-to-B2 structural transitions in rock salt intergrowth structures

Year: 2011 DOI: 10.1021/ic201901a

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Takafumi Yamamoto, Yoji Kobayashi, Taku Okada, Takehiko Yagi, Takateru Kawakami, Cédric Tassel, Shota Kawasaki, Naoyuki Abe, Ken Niwa, Takumi Kikegawa, Naohisa Hirao, Mikio Takano, Hiroshi Kageyama.   Inorganic Chemistry, 2011, 50, 11704-11787.


The rock salt (B1) structure of binary oxides or chalcogenides transforms to the CsCl (B2) structure under high pressure, with critical pressures P(s) depending on the cation to anion size ratio (R(c)/R(a)). We investigated structural changes of A(2)MO(3) (A = Sr, Ca; M = Cu, Pd) comprising alternate 7-fold B1 AO blocks and corner-shared MO(2) square-planar chains under pressure. All of the examined compounds exhibit a structural transition at P(s) = 29-41 GPa involving a change in the A-site geometry to an 8-fold B2 coordination. This observation demonstrates, together with the high pressure study on the structurally related Sr(3)Fe(2)O(5), that the B1-to-B2 transition generally occurs in these intergrowth structures. An empirical relation of P(s) and the R(c)/R(a) ratio for the binary system holds well for the intergrowth structure also, which means that P(s) is predominantly determined by the rock salt blocks. However, a large deviation from the relation is found in LaSrNiO(3.4), where oxygen atoms partially occupy the apical site of the MO(4) square plane. We predict furthermore the occurrence of the same structural transition for Ruddlesden-Popper-type layered perovskite oxides (AO)(AMO(3))(n), under higher pressures. For investigating the effect on the physical properties, an electrical resistivity of Sr(2)CuO(3) is studied.[on SciFinder (R)]