Charge disproportionation and site-selective local magnetic moments in the post-perovskite-type Fe2O3 under ultra-high pressures
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Abstract
Abstract The archetypal 3d Mott insulator hematite, Fe2O3, is one of the basic oxide components playing an important role in mineralogy of Earth’s lower mantle. Its high pressure–temperature behavior, such as the electronic properties, equation of state, and phase stability is of fundamental importance for understanding the properties and evolution of the Earth’s interior. Here, we study the electronic structure, magnetic state, and lattice stability of Fe2O3 at ultra-high pressures using the density functional plus dynamical mean-field theory (DFT + DMFT) approach. In the vicinity of a Mott transition, Fe2O3 is found to exhibit a series of complex electronic, magnetic, and structural transformations. In particular, it makes a phase transition to a metal with a post-perovskite crystal structure and site-selective local moments upon compression above 75 GPa. We show that the site-selective phase transition is accompanied by a charge disproportionation of Fe ions, with Fe3±δ and δ ~ 0.05–0.09, implying a complex interplay between electronic correlations and the lattice. Our results suggest that site-selective local moments in Fe2O3 persist up to ultra-high pressures of ~200–250 GPa, i.e., sufficiently above the core–mantle boundary. The latter can have important consequences for understanding of the velocity and density anomalies in the Earth’s lower mantle.
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Research context
OpenAlex topics: High-pressure geophysics and materials · Magnetic Properties and Synthesis of Ferrites · Iron oxide chemistry and applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (69)
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