Influence of Au, Ag, and Cu Adatoms on Optical Properties of TiO2 (110) Surface: Predictions from RT-TDDFT Calculations

In this paper, real-time time-dependent density-functional theory (RT-TDDFT) calculations are performed to analyze the optical property and charge transitions of a single noble metal atom deposited on rutile TiO₂ (110) surface. The model structures are built reflecting the equilibrium positions of deposited adatoms atop the TiO₂ surface. The absorption spectra are calculated for all model structures under study. To provide deeper insight into photo-absorption processes, the transition contribution maps are computed for the states of deposited adatoms involved in transitions. Assuming the photon energy is enough to overcome the band gap of TiO₂ (∼3 eV), the photogenerated electrons of TiO₂ seem to be partly accumulated around deposited Au atoms. In contrast, this is rarely observed for deposited Ag and Cu atoms. Based on our calculations, we have identified the transition state mechanism that is important for the design strategy of future photocatalytic materials.