Structural and spin transitions in Fe$_{2}$O$_{3}$

TL;DR

This study uses first principles calculations to explore pressure-induced structural and magnetic phase transitions in Fe₂O₃, revealing a sequence of magnetic and structural changes up to extremely high pressures.

Contribution

It provides detailed predictions of pressure-driven phase transitions and magnetic states in Fe₂O₃, identifying new stable phases and their properties under extreme conditions.

Findings

Transition from antiferromagnetic insulator to low-spin phase at ~38 GPa

Emergence of Rh₂O₃(II)-type structure as stable phase at high pressure

Development of a nonmagnetic Pmc2₁ phase at ~330 GPa and stability of Pbnm phase at ~880 GPa

Abstract

First principles density functional calculations for Fe$_{2}$O$_{3}$ has been performed over a wide range of pressures. The ground state is corundum-type hematite and is an antiferromagnetic insulator. This is in good agreement with experiment and other theoretical studies. On increasing pressure, the ground-state high-spin magnetic phase transforms to low spin via the closure of the charge transfer gap. The system also evolves to a new orthorhombic structure. Distorted corundum or Rh$_{2}$O$_{3}$(II) type structure with Pbcn symmetry and Pbnm type perovskite structure are two known competitive candidates for this structural phase, based on {\it single}--cationic type and {\it two}--cationic type picture, respectively. In our calculations, at about 38 GPa, Rh$_{2}$O$_{3}$(II) type structure becomes more stable with respect to the ground state hematite. Relative stability of Pbnm type perovskite is ruled out by our calculations in this pressure regime. The Rh$_{2}$O$_{3}$(II) type structure remains in its low spin state, with 1 $\mu_{B}/$Fe atom, up to about 120 GPa. At this pressure the nonmagnetic solution in Rh$_{2}$O$_{3}$(II) type structure becomes more favorable with respect to the low spin one. By further increasing the pressure at about 330 GPa, the system evolves to yet another new structural phase. This new orthorhombic structural phase is nonmagnetic and has Pmc2$_{1}$ symmetry, a subgroup of Cmcm. Surprisingly, on furthering rising the pressure, a Pbnm type nonmagnetic solution becomes competitive with the Pmc2$_{1}$ type structure and finally becomes stable at about 880 GPa.