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

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Abstract

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 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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Acknowledgments

All calculations have been performed using the Quantum-ESPRESSO distribution (Giannozzi et al. 2009). Charge densities were visualized using XCrySDen software (Kokalj 2003). Research was supported by NSF grants NSF/EAR 0635990 and NSF/ATM 0428774 (VLab). Computations were performed at the Minnesota Supercomputing Institute.

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Authors and Affiliations

  1. Department of Geology and Geophysics, University of Minnesota, Minneapolis, MN, 55455, USA

    Koichiro Umemoto

  2. Minnesota Supercomputing Institute and Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN, 55455, USA

    Renata M. Wentzcovitch

  3. Interactive Research Center of Science, Tokyo Institute of Technology, Meguro-ku, Tokyo, 152-8551, Japan

    Renata M. Wentzcovitch

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  1. Koichiro Umemoto
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Correspondence to Koichiro Umemoto.

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269_2010_412_MOESM1_ESM.doc

SFig. 1 Logarithmic derivatives of atomic radial wavefunctions at r = 1.06 Å. for yttrium, rhodium, and indium and at r = 0.79 Å. for oxygen. Thin solid and bold dashed lines are logarithmic derivations of all-electron and pseudo wave functions, respectively. They are indistinguishable (DOC 111 kb)

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Umemoto, K., Wentzcovitch, R.M. Effect of the d electrons on phase transitions in transition-metal sesquioxides. Phys Chem Minerals 38, 387–395 (2011). https://doi.org/10.1007/s00269-010-0412-1

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