High Pressure Structural Instability and Thermal Properties of Rutile TiO2 from First-principles

We report a first-principles calculation to investigate the structural instability of rutile TiO2. The high pressure structural parameters are well reproduced. The calculated phonon dispersion curves agree with experiments at zero pressure. Under compression, we capture a large softening around F point, which indicates the structural instability. From the high pressure elastic constants, we find that the rutile TiO2 is unstable when the applied pressure is larger than 17.7 GPa. Within the quasi-harmonic approximation, the thermal equation of state, thermal expansion coefficient, bulk modulus, and entropy are well reproduced. The thermal properties confirm the available experimental data and are extended to a wider pressure and temperature range.