Phase Transitions of AlFeO₃ and GaFeO₃ from the Chiral Orthorhombic (<i>Pna</i>2₁) Structure to the Rhombohedral (<i>R</i>3̅<i>c</i>) Structure

AlFeO(3) and GaFeO(3), which crystallize in a chiral orthorhombic (Pna2(1)) structure, transform to a rhombohedral (R3c) structure when subjected to ball-milling. There is a distinct difference between the transformations of AlFeO(3) and GaFeO(3). AlFeO(3) first transforms to an orthorhombic P2(1)2(1)2(1) structure followed by its transformation to the R3c structure, while GaFeO(3) goes directly to the R3c structure. The transformations have been characterized by X-ray diffraction and Raman spectroscopy. Magnetic properties of Pna2(1) and the transformed phases show significant differences. It is noteworthy that partial substitution of aluminum by gallium in AlFeO(3) as in Al(0.5)Ga(0.5)FeO(3) eliminates the intermediate P2(1)2(1)2(1) phase, causing direct transformation of the Pna2(1) structure to the R3c structure. All of the transformations are thermodynamically first-order associated with significant changes in volume. We have used first-principles simulations to determine the pressure-dependent properties of AlFeO(3) and GaFeO(3) in orthorhombic and corundum structures and have estimated the critical pressures for the structural phase transition between the two structures. On the basis of this information, we also comment on the differences in the behavior of AlFeO(3) and GaFeO(3) under ball-milling.