Effect of the d electrons on phase transitions in transition-metal sesquioxides

We present a systematic density-functional study of phase relations in three 4d-transition-metal sesquioxides: Y2O3, Rh2O3, and In2O3. Y2O3 and In2O3 undergo pressure-induced transitions to phases with larger cation coordination number (from 6 to 7) at low pressures. However, this does not occur in Rh2O3 at least up to *300 GPa. This cannot be explained by usual arguments based on ionic-radii ratios often used successfully to explain phase relations in simple-metal and rare-earth sesquioxides and sesquisulfides. Inspection of their electronic structures shows that, in Rh2O3, the electronic occupancy of 4d orbitals, 4d, plays a fundamental role in the extraordinary stability of the Rh2O3(II)-type phase with respect to coordination increase. We point out that d-orbital occupancy is a fundamental factor in explaining phase relations in transition-metal sesquioxides and sesquisulfides.