Ligand-hole localization in oxides with unusual valence Fe

Abstract

Unusual high-valence states of iron are stabilized in a few oxides. A-site-ordered perovskite-structure oxides contain such iron cations and exhibit distinct electronic behaviors at low temperatures, e.g. charge disproportionation (4Fe 4+ → 2Fe 3+ + 2Fe 5+) in CaCu 3Fe 4O 12 and intersite charge transfer (3Cu 2+ + 4Fe 3.75+ → 3Cu 3+ + 4Fe 3+) in LaCu 3Fe 4O 12. Here we report the synthesis of solid solutions of CaCu 3Fe 4O 12 and LaCu 3Fe 4O 12 and explain how the instabilities of their unusual valence states of iron are relieved. Although these behaviors look completely different from each other in simple ionic models, they can both be explained by the localization of ligand holes, which are produced by the strong hybridization of iron d and oxygen p orbitals in oxides. The localization behavior in the charge disproportionation of CaCu 3Fe 4O 12 is regarded as charge ordering of the ligand holes, and that in the intersite charge transfer of LaCu 3Fe 4O 12 is regarded as a Mott transition of the ligand holes.