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We apply the frozen density embedding method, using a full relaxation of embedded densities through a freeze-and-thaw procedure, to study the electronic structure of several benchmark ground-state charge-transfer complexes, in order to assess the merits and limitations of the approach for this class of systems. The calculations are performed using both semilocal and hybrid exchange-correlation (XC) functionals. The results show that embedding calculations using semilocal XC functionals yield rather large deviations with respect to the corresponding supermolecular calculations. Due to a large error cancellation effect, however, they can often provide a relatively good description of the electronic structure of charge-transfer complexes, in contrast to supermolecular calculations performed at the same level of theory. On the contrary, when hybrid XC functionals are employed, both embedding and supermolecular calculations agree very well with each other and with the reference benchmark results. In conclusion, for the study of ground-state charge-transfer complexes via embedding calculations hybrid XC functionals are the method of choice due to their higher reliability and superior performance. [ABSTRACT FROM AUTHOR]

Titanium dioxide (TiO2) has rich physical properties with potential implications for both fundamental physics and new applications. To date, the main focus of applied research is to tune its optical properties, which is usually done via doping and/or nanoengineering. However, understanding the role of d electrons in materials and possible functionalization of d-electron properties are still major challenges. Herewith, within a combination of an innovative experimental technique, high-energy optical conductivity, and state-of-the-art ab initio electronic structure calculations, we report an emerging, novel resonant exciton in the deep ultraviolet region of the optical response. The resonant exciton evolves upon low-concentration Ta substitution in anatase TiO2 films. It is surprisingly robust and related to strong electron-electron and electron-hole interactions. The d- and f-orbital localization, due to Ta substitution, plays an unexpected role, activating strong electronic correlations and dominating the optical response under photoexcitation. Our results shed light on a new optical phenomenon in anatase TiO2 films and on the possibility of tuning electronic properties by Ta substitution. [ABSTRACT FROM AUTHOR]