Pressure-induced coordination crossover in magnetite, a high pressure Mössbauer study

M. P. Pasternak*, W. M. Xu, G. Kh Rozenberg, R. D. Taylor, R. Jeanloz

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

21 Scopus citations

Abstract

Temperature-dependent 57Fe Mössbauer spectroscopy to 40 GPa shows that Fe3O4 magnetite undergoes a coordination crossover (CC) whereby charge-density is shifted from octahedral to tetrahedral sites and the spinel structure thus changes from inverse to normal with increasing pressure and decreasing temperature. A precursor to the CC is a d-charge decoupling within the octahedral sites at the inverse spinel phase. The CC-transition takes place almost exactly at the Verwey transition temperature (TV=122K) at ambient pressure. While TV decreases with pressure, the CC-transition temperature increases with pressure, reaching 350 K at 10 GPa. The d electron localization mechanism proposed by Verwey and later by Mott for T<TV is shown to be unrelated to the actual mechanism of the metal-insulator transition attributed to the Verwey transition. It is proposed that a first-order phase transition taking place at ∼TV at ambient pressure opens a small gap within the oxygen p-band, resulting in the observed insulating state at T>TV.

Original languageEnglish
Pages (from-to)1531-1535
Number of pages5
JournalJournal of Physics and Chemistry of Solids
Volume65
Issue number8-9
DOIs
StatePublished - Aug 2004

Funding

FundersFunder number
United States-Israel Binational Science Foundation9800003
Israel Science Foundation1998003

    Keywords

    • C. High pressure
    • C. Mössbauer spectroscopy
    • C. X-ray diffraction

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