Magnetism and the Trimeron Bond

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A review of progress in understanding the Verwey transition in magnetite (Fe3O4) over the past decade is presented. This electronic and structural transition at TV ≈ 125 K was reported in 1939 and has since been a contentious issue in magnetism. Long range Fe2+/Fe3+ charge ordering has been confirmed below the transition from crystal structure refinement, and Fe2+ orbital ordering and formation of trimerons through weak bonding of Fe2+ states to two Fe neighbors has been discovered. This model has accounted for many spectroscopic observations such as the 57Fe NMR frequencies. The trimeron lifetime has been measured, and trimeron soft modes have been observed. The origin of the first to second order crossover of Verwey transitions in doped magnetites has been revealed by a nanoparticle study. Electronic and structural fluctuations are found to persist to temperatures far above TV and local structural distortions track the bulk magnetization, disappearing at the 850 K Curie transition. New binary mixed-valent iron oxides discovered at high pressure are found to have electronic transitions and orbital molecule ground states similar to those of magnetite.
Original languageEnglish
JournalChemistry of Materials
Early online date30 Mar 2022
Publication statusE-pub ahead of print - 30 Mar 2022


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