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Phase stability and pressure-induced structural transitions at zero temperature in ZnSiO3 and Zn2SiO4

S Zh Karazhanov1,2,3,5, P Ravindran1, P Vajeeston1, A G Ulyashin2,6, H Fjellvåg1 and B G Svensson4

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Using density functional total energy calculations the structural phase stability and pressure-induced structural transition in different polymorphs of ZnSiO3 and Zn2SiO4 have been studied. Among the considered monoclinic phase with space groups (P 21/c) and (C 2/c), rhombohedral (R\bar {3}) and orthorhombic (Pbca) modifications the monoclinic phase (P 21/c) of ZnSiO3 is found to be the most stable one. At high pressure monoclinic ZnSiO3 (C 2/c) can co-exist with orthorhombic (Pbca) modification. Differences in equilibrium volume and total energy of these two polymorphs are very small, which indicates that it is relatively easier to transform between these two phases by temperature, pressure or chemical composition. It can also explain the experimentally established result of metastability of the orthorhombic phase under all conditions. The following sequence of pressure-induced structural phase transitions is found for ZnSiO3 polymorphs: monoclinic (P2_{1}/c) \to monoclinic (C2/c) \to rhombohedral (R\bar {3}) . Among the rhombohedral (R\bar {3} ), tetragonal (I\bar {4} 2d) , orthorhombic (Pbca), orthorhombic (Imma), cubic (Fd\bar {3} m) and orthorhombic (Pbnm) modifications of Zn2SiO4, the rhombohedral phase is found to be the ground state. For this chemical composition of zinc silicate the following sequence of structural phase transitions is found: rhombohedral (R\bar {3}) \to tetragonal (I\bar {4} 2d) \to orthorhombic (Pbca) \to orthorhombic (Imma) \to cubic (Fd\bar {3} m) \to orthorhombic (Pbnm). Based on the analogy of crystal structures of magnesium and zinc silicates and using the lattice and positional parameters of Mg2SiO4 as input, structural properties of spinel Zn2SiO4 have also been studied.


PACS

62.50.-p High-pressure effects in solids and liquids

61.50.Ks Crystallographic aspects of phase transformations; pressure effects

71.20.Ps Other inorganic compounds

61.66.Fn Inorganic compounds

71.15.Mb Density functional theory, local density approximation, gradient and other corrections

64.70.K- Solid–solid transitions

Subjects

Condensed matter: electrical, magnetic and optical

Condensed matter: structural, mechanical & thermal

Dates

Issue 48 (2 December 2009)

Received 8 September 2009, in final form 19 October 2009

Published 6 November 2009



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