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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Abstract

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
Volume9
Issue number1
Number of pages11
ISSN2041-1723
DOIs
Publication statusPublished - 2018

Cite this

Ovsyannikov, S. V., Bykov, M., Bykova, E., Glazyrin, K., Manna, R. S., Tsirlin, A. A., ... Dubrovinsky, L. S. (2018). Pressure tuning of charge ordering in iron oxide. Nature Communications, 9(1), [4142]. https://doi.org/10.1038/s41467-018-06457-x
Ovsyannikov, Sergey V. ; Bykov, Maxim ; Bykova, Elena ; Glazyrin, Konstantin ; Manna, Rudra Sekhar ; Tsirlin, Alexander A. ; Cerantola, Valerio ; Kupenko, Ilya ; Kurnosov, Alexander V. ; Kantor, Innokenty ; Pakhomova, Anna S. ; Chuvashova, Irina ; Chumakov, Aleksandr I. ; Ruffer, Rudolf ; McCammon, Catherine ; Dubrovinsky, Leonid S. / Pressure tuning of charge ordering in iron oxide. In: Nature Communications. 2018 ; Vol. 9, No. 1.
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title = "Pressure tuning of charge ordering in iron oxide",
abstract = "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.",
author = "Ovsyannikov, {Sergey V.} and Maxim Bykov and Elena Bykova and Konstantin Glazyrin and Manna, {Rudra Sekhar} and Tsirlin, {Alexander A.} and Valerio Cerantola and Ilya Kupenko and Kurnosov, {Alexander V.} and Innokenty Kantor and Pakhomova, {Anna S.} and Irina Chuvashova and Chumakov, {Aleksandr I.} and Rudolf Ruffer and Catherine McCammon and Dubrovinsky, {Leonid S.}",
year = "2018",
doi = "10.1038/s41467-018-06457-x",
language = "English",
volume = "9",
journal = "Nature Communications",
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Ovsyannikov, SV, Bykov, M, Bykova, E, Glazyrin, K, Manna, RS, Tsirlin, AA, Cerantola, V, Kupenko, I, Kurnosov, AV, Kantor, I, Pakhomova, AS, Chuvashova, I, Chumakov, AI, Ruffer, R, McCammon, C & Dubrovinsky, LS 2018, 'Pressure tuning of charge ordering in iron oxide', Nature Communications, vol. 9, no. 1, 4142. https://doi.org/10.1038/s41467-018-06457-x

Pressure tuning of charge ordering in iron oxide. / Ovsyannikov, Sergey V.; Bykov, Maxim; Bykova, Elena; Glazyrin, Konstantin; Manna, Rudra Sekhar; Tsirlin, Alexander A.; Cerantola, Valerio; Kupenko, Ilya; Kurnosov, Alexander V.; Kantor, Innokenty; Pakhomova, Anna S.; Chuvashova, Irina; Chumakov, Aleksandr I.; Ruffer, Rudolf; McCammon, Catherine; Dubrovinsky, Leonid S.

In: Nature Communications, Vol. 9, No. 1, 4142, 2018.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Pressure tuning of charge ordering in iron oxide

AU - Ovsyannikov, Sergey V.

AU - Bykov, Maxim

AU - Bykova, Elena

AU - Glazyrin, Konstantin

AU - Manna, Rudra Sekhar

AU - Tsirlin, Alexander A.

AU - Cerantola, Valerio

AU - Kupenko, Ilya

AU - Kurnosov, Alexander V.

AU - Kantor, Innokenty

AU - Pakhomova, Anna S.

AU - Chuvashova, Irina

AU - Chumakov, Aleksandr I.

AU - Ruffer, Rudolf

AU - McCammon, Catherine

AU - Dubrovinsky, Leonid S.

PY - 2018

Y1 - 2018

N2 - 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.

AB - 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.

U2 - 10.1038/s41467-018-06457-x

DO - 10.1038/s41467-018-06457-x

M3 - Journal article

VL - 9

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

IS - 1

M1 - 4142

ER -

Ovsyannikov SV, Bykov M, Bykova E, Glazyrin K, Manna RS, Tsirlin AA et al. Pressure tuning of charge ordering in iron oxide. Nature Communications. 2018;9(1). 4142. https://doi.org/10.1038/s41467-018-06457-x