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Jahn-Teller Distortions, Cation Ordering and Octahedral Tilting in Perovskites
Chemistry Faculty Research and Scholarship
  • Michael W Lufaso, University of North Florida
  • Patrick M Woodward
Document Type
Article
Publication Date
2-1-2004
Disciplines
Abstract

In transition metal oxides, preferential occupation of specific d orbitals on the transition metal ion can lead to the development of a long-range ordered pattern of occupied orbitals. This phenomenon, referred to as orbital ordering, is usually observed indirectly from the cooperative Jahn-Teller distortions (CJTDs) that result as a consequence of the orbital ordering. This paper examines the interplay between orbital ordering, octahedral tilting and cation ordering in perovskites. Both ternary AMX3 perovskites containing an active Jahn-Teller (J-T) ion on the octahedral site and quaternary A2MM'X6 perovskites containing a J-T ion on one-half of the octahedral sites have been examined. In AMX3 perovskites, the tendency is for the occupied 3d3x2-r2 and 3d3z2-r2 orbitals to order in the ac plane, as exemplified by the crystal structures of LaMnO3 and KCuF3. This arrangement maintains a favorable coordination environment for the anion sites. In AMX3 perovskites, octahedral tilting tends to enhance the magnitude of the J-T distortions. In A2MM'X6 perovskites, the tendency is for the occupied 3d3z2-r2 orbitals to align parallel to the c axis. This pattern maintains a favorable coordination environment about the symmetric M'-cation site. The orbital ordering found in rock-salt ordered A2MM'X6 perovskites is compatible with octahedral rotations about the c axis (Glazer tilt system a0a0c-) but appears to be incompatible with GdFeO3-type octahedral tilting (tilt system a-b+a-).

Comments

Originally published in Acta Crystallographica Section B-Structural Science 2004, 60, 10-20

http://dx.doi.org/10.1107/S0108768103026661

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In Copyright
Citation Information
Michael W Lufaso and Patrick M Woodward. "Jahn-Teller Distortions, Cation Ordering and Octahedral Tilting in Perovskites" (2004)
Available at: http://works.bepress.com/michael_lufaso/4/