Journal
PHYSICS AND CHEMISTRY OF MINERALS
Volume 38, Issue 5, Pages 387-395Publisher
SPRINGER
DOI: 10.1007/s00269-010-0412-1
Keywords
Phase transition; Sesquioxides; d-orbital occupancy; Electronic structure; First-principles calculation
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Funding
- NSF [NSF/EAR 0635990, NSF/ATM 0428774]
- Directorate For Geosciences
- Division Of Earth Sciences [0810272, 1019853] Funding Source: National Science Foundation
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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 similar 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 (6), 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.
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