Exploring the A+B5+O3 compounds

doi:10.1016/S0022-4596(73)80005-2

Journal of Solid State Chemistry

Volume 6, Issue 4, April 1973, Pages 493-501

https://doi.org/10.1016/S0022-4596(73)80005-2 Get rights and content

The several structures exhibited by A⁺B⁵⁺O₃ compositions having B = Nb, Ta, Sb or Bi are summarized. New phases, prepared either by high-pressure techniques or by ion exchange, are included. Their stability is interpreted qualitatively in terms of four principal factors: relative ionic sizes, Madelung energy, polarizability of A-cation cores, and the covalent contribution to the B-0 bonds. This latter contribution inhibits the formation of 180° Sb-O-Sb or Bi-O-Bi bond angles, whereas electrostatic forces inhibit the formation of Sb-Sb or Bi-Bi pairs in octahedral sites sharing a common face. A strong π-bond contribution to the B-O covalency weakens both these constraints for Nb⁵⁺ and Ta⁵⁺ ions. A criterion for ferroelectric distortions of the cubic-perovskite phase is presented, and evidence for polarizability of the 3d¹⁰ and 4d¹⁰ cores of Cu⁺ and Ag⁺ ions is cited.

References (21)

J.M. Longo et al.
Mater. Res. Bull.
(1969)
P. Bailey
E.F. Bertaut et al.
J. Phys. Chem. Solids
(1961)
A.W. Sleight et al.
Mater. Res. Bull.
(1970)
H.Y-P. Hong
Lincoln Laboratory Solid State Research Report
(May 10, 1972)
M. Edstrand et al.
Acta Chem. Scand.
(1954)
P. Spiegelberg
Ark. Kemi. Mineral. Geol.
(1940)
J.B. Goodenough et al.
Landolt-Bornstein Tabellen
R.D. Shannon et al.
Acta Crystallogr.
(1969)
L. Katz et al.
Inorg. Chem.
(1964)
J.G. Dickinson et al.
J. Am. Chem. Soc.
(1961)
P.C. Donahue et al.
Inorg. Chem.
(1965)
P.C. Donahue et al.
Inorg. Chem.
(1966)

There are more references available in the full text version of this article.

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^*: This work was sponsored by the Department of the Air Force.

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Exploring the A+B5+O3 compounds*

Mater. Res. Bull.

J. Phys. Chem. Solids

Mater. Res. Bull.

Lincoln Laboratory Solid State Research Report

Acta Chem. Scand.

Ark. Kemi. Mineral. Geol.

Landolt-Bornstein Tabellen

Acta Crystallogr.

Inorg. Chem.

J. Am. Chem. Soc.

Inorg. Chem.

Inorg. Chem.

Exploring the A⁺B⁵⁺O₃ compounds*