Theoretical study on martensitic-type transformation path from rutile phase to α-PbO2 phase of Ti2O**Project supported by the National Natural Science Foundation of China (Grant Nos. 51872227, 51572219, and 11447030).

Abstract

The martensitic-type phase transformation paths from the rutile to the α-PbO2 phase of TiO2 are studied with linear interpolation and NEB/G-SSNEB methods based on first-principles calculations. Its potential energy surface and the lowest energy path are revealed. Our results indicate that the titanium atoms of the rutile phase shuffle along the [0–11]rut crystal direction to form the α-PbO2 phase. During the phase transition, the oxygen atoms are dragged by the heavier titanium atoms and then reach their new equilibrium positions. The barrier of phase transition from nudged elastic band theory is about 231 meV, which is qualitatively consistent with previous theoretical calculations from the monoclinic phase to the tetragonal phase for ZrO2 and HfO2. Debye model can also be successfully used to predict the pressure and temperature of the phase transformation.