Conductivity and 'negative U' for ionic grain boundaries

Abstract
The authors show that charge-transfer excitations (like 2M2+ to M++M3+) can be lowered greatly in energy near grain boundaries, where sites are no longer equivalent. In special cases the excitations may be exothermic ('negative-U' behaviour); likely cases include (320) and (122) grain boundaries in FeO. Consequences include effects on conductivity, segregation of impurities with different valence, and on other charge-state-dependent properties.

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