The Stability, Electronic Structure, and Optical Property of TiO2 Polymorphs

Abstract

Phonon density of states calculation shows that a new TiO2 polymorph with tridymite structure is mechanically stable. Enthalpies of 9 TiO2 polymorphs under different pressure are presented to study the relative stability of the TiO2 polymorphs. Band structures for the TiO2 polymorphs are calculated by density functional theory with generalized gradient approximation and the band energies at high symmetry k-points are corrected using the GW method to accurately determine the band gap. The differences between direct band gap energies and indirect band gap energies are very small for rutile, columbite and baddeleyite TiO2, indicating a quasi-direct band gap character. The band gap energies of baddeleyite (quasi-direct) and brookite (direct) TiO2 are close to that of anatase (indirect) TiO2. The band gap of the newly predicted tridymite-structured TiO2 is wider than the other 8 polymorphs. For optical response calculations, two-particle effects have been included by solving the Bethe-Salpeter equation for Coulomb correlated electron-hole pairs. TiO2 with cotunnite, pyrite, and fluorite structures have optical transitions in the visible light region.