B1-to-B2 structural transitions in rock salt intergrowth structures.
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.
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo, Kyoto 615-8510, Japan.
Takafumi
T
Yamamoto
Yoji
Y
Kobayashi
Taku
T
Okada
Takehiko
T
Yagi
Takateru
T
Kawakami
Cédric
C
Tassel
Shota
S
Kawasaki
Naoyuki
N
Abe
Ken
K
Niwa
Takumi
T
Kikegawa
Naohisa
N
Hirao
Mikio
M
Takano
Hiroshi
H
Kageyama
D002118:Calcium / Q000737:chemistry; D002586:Cesium / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D010087:Oxides / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry; D011312:Pressure; D012492:Salts / Q000737:chemistry*; D013324:Strontium / Q000737:chemistry
D002712:Chlorides; D010087:Oxides; D012492:Salts; D002586:Cesium; D010165:Palladium; D003300:Copper; C028019:cesium chloride; D002118:Calcium; D013324:Strontium