Characterization of the TiSiO4 structure and its pressure-induced phase transformations: density functional theory study

Abstract

Theoretical investigations concerning the possible titanium silicate polymorphs have been performed using density functional theory at B3LYP level. Total-energy calculations and geometry optimizations have been carried out for all phases involved. The following sequence of pressure-driven structural transitions has been found: CrVO4 -type, Cmcm in parenthesis the transition pressure , → zircon-type, I41 / amd 0.8 GPa , → scheelite-type, I41 / a 3.8 GPa . At higher pressure the last phase is found to be stable at least up to 25 GPa. The equation of state of the different polymorphs is also reported. We found that the highest bulk modulus corresponds to the zircon and scheelite phases with values of 248 and 238 GPa, respectively. The orthorhombic Cmcm phase is the most compressible of all the studied structures with a bulk modulus of 124 GPa, being also the most stable phase at ambient pressure. Finally, calculations of the electronic structure, vibrational and dielectric properties of TiSiO4 are also reported