Order-disorder in grossly non-stoichiometric SrFeO2.50 -: a simulation study

被引:31
作者
Bakken, E
Allan, NL
Barron, THK
Mohn, CE
Todorov, IT
Stolen, S
机构
[1] Univ Oslo, Dept Chem, N-0315 Oslo, Norway
[2] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
关键词
D O I
10.1039/b300137g
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Configurational lattice energy techniques are used to investigate oxygen vacancy ordering and the order disorder transition in SrFeO2.50. Vacancy disorder is shown to present many new challenges, largely due to the extensive relaxation in such grossly non-stoichiometric systems. With large supercells it is not feasible to optimise each individual configuration. Efficient methods for choosing a small number of representative configurations are discussed. Oxygen vacancy-vacancy interactions are considerable in SrFeO2.50 and lead to the formation of preferred local structural entities. While the low-temperature structure consists of an ordered arrangement of octahedra and tetrahedra, the disordered high-temperature structure may be described as a mixture of tetrahedra, square pyramids and octahedra. Fe atoms with coordination numbers lower than four are negligible. The assumption of an ideal solution of oxygen vacancies in such systems, commonly made in standard thermodynamic treatments, is questionable.
引用
收藏
页码:2237 / 2243
页数:7
相关论文
共 26 条
[1]   Ionic solids at elevated temperatures and/or high pressures:: lattice dynamics, molecular dynamics, Monte Carlo and ab initio studies [J].
Allan, NL ;
Barrera, GD ;
Purton, JA ;
Sims, CE ;
Taylor, MB .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2000, 2 (06) :1099-1111
[2]   Free energy of solid solutions and phase diagrams via quasiharmonic lattice dynamics [J].
Allan, NL ;
Barrera, GD ;
Fracchia, RM ;
Lavrentiev, MY ;
Taylor, MB ;
Todorov, IT ;
Purton, JA .
PHYSICAL REVIEW B, 2001, 63 (09)
[3]   Ab initio calculation of phase diagrams of ceramics and minerals [J].
Allan, NL ;
Barrera, GD ;
Lavrentiev, MY ;
Todorov, IT ;
Purton, JA .
JOURNAL OF MATERIALS CHEMISTRY, 2001, 11 (01) :63-68
[4]   PREPARATION AND CRYSTAL-STRUCTURE OF THE DEFICIENT PEROVSKITE LANIO2.5, SOLVED FROM NEUTRON POWDER DIFFRACTION DATA [J].
ALONSO, JA ;
MARTINEZLOPE, MJ .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1995, (17) :2819-2824
[5]   Redox energetics of perovskite-related oxides [J].
Bakken, E ;
Norby, T ;
Stolen, S .
JOURNAL OF MATERIALS CHEMISTRY, 2002, 12 (02) :317-323
[6]   The crystal structures, microstructure and ionic conductivity of Ba2In2O5 and Ba(InxZr1-x)O3-x/2 [J].
Berastegui, P ;
Hull, S ;
García-García, FJ ;
Eriksson, SG .
JOURNAL OF SOLID STATE CHEMISTRY, 2002, 164 (01) :119-130
[7]   REFINEMENT OF CRYSTAL-STRUCTURE OF DICALCIUM FERRITE, CA2FE2O5 [J].
BERGGREN, J .
ACTA CHEMICA SCANDINAVICA, 1971, 25 (10) :3616-&
[8]   SR2MN2O5, AN OXYGEN-DEFECT PEROVSKITE WITH MN(III) IN SQUARE PYRAMIDAL COORDINATION [J].
CAIGNAERT, V ;
NGUYEN, N ;
HERVIEU, M ;
RAVEAU, B .
MATERIALS RESEARCH BULLETIN, 1985, 20 (05) :479-484
[9]  
CATLOW CRA, 1982, COMPUTER SIMULATION, P3
[10]   THEORY OF THE DIELECTRIC CONSTANTS OF ALKALI HALIDE CRYSTALS [J].
DICK, BG ;
OVERHAUSER, AW .
PHYSICAL REVIEW, 1958, 112 (01) :90-103