Electronic hole localization in rutile and anatase TiO2 - Self-interaction correction in Δ-SCF DFT

We study electronic hole localization in rutile and anatase titanium dioxide by means of Delta-Self-Consistent Field Density Functional Theory. In order to compare stabilities of the localized and the delocalized hole states we introduce a simple correction to the wrong description of the localization processes within DFT. The correction removes the non-linearity of energy for fractional excitations. We show that the self-trapped and the delocalized hole states have comparable stability in rutile TiO2 whereas in anatase the former is favoured. The theoretical prediction of the adiabatic Potential Energy Surfaces for the hole localization compares well with published photoluminescence measurements. (C) 2011 Elsevier B.V. All rights reserved.