Xu, Stokes, Dong - 2010 - First-principles calculation of kinetic barriers and metastability for the corundum-to-Rh 2 O 3 (II) transition in Al 2 O 3.pdf
Theoretical or Mathematical/ ab initio calculations; corundum; crystal symmetry; elastic constants; enthalpy; high-pressure solid-state phase transformations; rhodium compounds; space groups/ first-principles calculation; kinetic barriers; metastability; rhombohedral corundum crystal; orthorhombic crystal; space group symmetry; corundum phase; enthalpy barrier; elastic properties; Bravais lattices; monoclinic unit cells; high-pressure phase transitions; Al/sub 2/O/sub 3// A6470K Solid-solid transitions A8130H Constant-composition solid-solid phase transformations: polymorphic, massive, and order-disorder A6550 Thermodynamic properties and entropy A6150E Crystal symmetry; models and space groups, and crystalline systems and classes A6220D Elasticity, elastic constants A8140J Elasticity and anelasticity A6250 High-pressure and shock-wave effects in solids and liquids/ Al2O3/bin Al2/bin O3/bin Al/bin O/bin
Abstract :
[en] We demonstrate that the rhombohedral corundum crystal and the orthorhombic Rh/sub 2/O/sub 3/ (II) crystal are structurally related by a diffusionless monoclinic common subgroup pathway, along which the intermediate structures have the space group P2/c symmetry. This transformation pathway is energetically favored because the majority of Al-O bonds are preserved during the transition. Only 1/3 of the four-coordinated anions and 1/2 of the six-coordinated cations break and reform a single bond. No other bonds are broken in the transformation. Our calculated forward (corundum-to-Rh/sub 2/O/sub 3/ (II)) enthalpy barrier (about 140 meV/atom) in Al/sub 2/O/sub 3/ is not pressure-sensitive at least up to 160 GPa, which is consistent with the observed metastability of the corundum phase around room temperature. In contrast, we predict a significantly decreasing backward (Rh/sub 2/O/sub 3/ (II)-to-corundum) enthalpy barrier on decompression, which suggests that the high-pressure Rh/sub 2/O/sub 3/ (II) phase of Al/sub 2/O/sub 3/ is unlikely to be recoverable at ambient conditions. In addition, we propose a general, common subgroup-based approach to compare elastic properties of two phases with different Bravais lattices. By treating both rhombohedral and orthorhombic phases with common monoclinic P2/c unit cells (non-primitive for the corundum phase), we show that the elastic properties of the high-pressure Rh/sub 2/O/sub 3/ (II) phase are very comparable to those of the ambient corundum phase.
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