Understanding the effects of Cr doping in rutile TiO₂ by DFT calculations and X-ray spectroscopy

The effects of Cr on local environment and electronic structure of rutile TiO₂ are studied combining theoretical and experimental approaches. Neutral and negatively charged substitutional Cr impurities Cr_Ti⁰ and Cr_Ti^1- as well as Cr-oxygen vacancy complex 2Cr_Ti + V_O are studied by the density functional theory (DFT) within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) functional. Experimental results based on X-Ray absorption spectroscopy (XAS) and X-Ray photoelectron spectroscopy (XPS) performed on Cr doped TiO₂ at the Synchrotron facility were compared to the theoretical results. It is shown that the electrons of the oxygen vacancy tend to be localized at the t_2g states of the Cr ions in order to reach the stable oxidation state of Cr³⁺. Effects of Cr on crystal field (CF) and structural distortions in the rutile TiO₂ cell were analyzed by the DFT calculations and XAS spectra revealing that the CF and tetragonal distortions in TiO₂ are very sensitive to the concentration of Cr.