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Magnetism and the Trimeron Bond.

John Paul Attfield
Published in: Chemistry of materials : a publication of the American Chemical Society (2022)
A review of progress in understanding the Verwey transition in magnetite (Fe 3 O 4 ) over the past decade is presented. This electronic and structural transition at T V ≈ 125 K was reported in 1939 and has since been a contentious issue in magnetism. Long range Fe 2+ /Fe 3+ charge ordering has been confirmed below the transition from crystal structure refinement, and Fe 2+ orbital ordering and formation of trimerons through weak bonding of Fe 2+ states to two Fe neighbors has been discovered. This model has accounted for many spectroscopic observations such as the 57 Fe 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 T V 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.
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