Pressure tuning of charge ordering in iron oxide

Sergey V. Ovsyannikov*, Maxim Bykov, Elena Bykova, Konstantin Glazyrin, Rudra Sekhar Manna, Alexander A. Tsirlin, Valerio Cerantola, Ilya Kupenko, Alexander V. Kurnosov, Innokenty Kantor, Anna S. Pakhomova, Irina Chuvashova, Aleksandr I. Chumakov, Rudolf Ruffer, Catherine McCammon, Leonid S. Dubrovinsky

*Corresponding author for this work

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A Verwey-type charge-ordering transition in magnetite at 120 K leads to the formation of linear units of three iron ions with one shared electron, called trimerons. The recently-discovered iron pentoxide (Fe4O5) comprising mixed-valent iron cations at octahedral chains, demonstrates another unusual charge-ordering transition at 150 K involving competing formation of iron trimerons and dimerons. Here, we experimentally show that applied pressure can tune the charge-ordering pattern in Fe4O5 and strongly affect the ordering temperature. We report two charge-ordered phases, the first of which may comprise both dimeron and trimeron units, whereas, the second exhibits an overall dimerization involving both the octahedral and trigonal-prismatic chains of iron in the crystal structure. We link the dramatic change in the charge-ordering pattern in the second phase to redistribution of electrons between the octahedral and prismatic iron chains, and propose that the average oxidation state of the iron cations can pre-determine a charge-ordering pattern.
Original languageEnglish
Article number4142
JournalNature Communications
Issue number1
Number of pages11
Publication statusPublished - 2018


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