Titanium dioxide (TiO₂) holds significant scientific and technological relevance as a key photocatalyst and resistive random-access memory, demonstrating unique physicochemical properties and serving as an n-type semiconductor. Understanding the density and arrangement of oxygen vacancies (VOs) is crucial for tailoring TiO₂’s properties to diverse technological needs, driving increased interest in exploring oxygen vacancy complexes and superstructures. In this mini review, we summarize the recent understandings of the fundamental properties of oxygen vacancies in bulk rutile (R-TiO₂) and anatase (A-TiO₂) based on DFT and beyond method. We specifically focus on the excess electrons and their spatial arrangement of disordered single VO in bulk R and A-TiO₂, aligned with the experimental findings. We also highlight the theoretical works on investigating the geometries and stabilities of ordered VOs complexes in bulk TiO₂. This comprehensive review provides insights into the fundamental properties of excess electrons in reduced TiO₂, offering valuable perspectives for future research and technological advancements in TiO₂-based devices.
