The electronic structure and optical response of rutile, anatase and brookite TiO2

Abstract

In this study, we present a combined density functional theory and many-body perturbation theory study on the electronic and optical properties of TiO2 brookite as well as the tetragonal phases rutile and anatase. The electronic structure and linear optical response have been calculated from the Kohn–Sham band structure applying (semi)local as well as nonlocal screened hybrid exchange–correlation density functionals. Single-particle excitations are treated within the GW approximation for independent quasiparticles. For optical response calculations, two-particle excitations have been included by solving the Bethe–Salpeter equation for Coulomb correlated electron–hole pairs. On this methodological basis, gap data and optical spectra for the three major phases of TiO2 are provided. The common characteristics of brookite with the rutile and anatase phases, which have been discussed more comprehensively in the literature, are highlighted. Furthermore, the comparison of the present calculations with measured optical response data of rutile indicate that discrepancies discussed in numerous earlier studies are due to the measurements rather than related to an insufficient theoretical description.