The photochemistry of TiO2 has been studied intensively since it was discovered that TiO2 can act as a photocatalyst. Nevertheless, it has proven difficult to establish the detailed charge-transfer processes involved, partly because the excited states involved are difficult to study. Here we present evidence of the existence of hydroxyl-induced excited states in the conduction band region. Using two-photon photoemission, we show that stepwise photoexcitation from filled band gap states lying 0.8 eV below the Fermi level of rutile TiO2(110) excites hydroxyl-induced states 2.73 eV above the Fermi level that has an onset energy of ∼3.1 eV. The onset is shifted to lower energy by the coadsorption of molecular water, which suggests a means of tuning the energy of the excited state.

Excess electrons facilitate redox reactions at the technologically relevant anatase TiO 2 (101) surface. The availability of these electrons is related to the defect concentration at the surface. We present two-photon (2PPE, 3.10-3.54 eV) and ultraviolet (UPS, 21.2 & 40.8 eV) photoemission spectroscopy measurements evidencing an increased concentration of excess electrons following electron bombardment at room temperature. Irradiationinduced surface oxygen vacancies are known to migrate into the sub-surface at this temperature, quickly equilibrating the surface defect concentration. Hence, we propose that the irradiated surface is hydroxylated. Peaks in UPS difference spectra are observed centred 8.45, 6.50 and 0.73 eV below the Fermi level, which are associated with the 3r and 1p hydroxyl molecular orbitals and Ti 3d band gap states, respectively. The higher concentration of excess electrons at the hydroxylated anatase (101) surface may increase the potential for redox reactions.

Time-resolved pump-probe photoemission spectroscopy has been used to study the dynamics of charge carrier recombination and trapping on hydroxylated rutile TiO 2 (110). Two types of pump excitation were employed, one in the infrared (0.95 eV) and the other in the UV (3.5 eV) region. With IR excitation, electrons associated with defects are excited into the bottom of the conduction band from the polaronic states within the band gap, which are retrapped within 45±10 fs. Under UV excitation, the electrons in these band gap state (BGS) and valence band electrons are excited into the conduction band. In addition to the fast polaron trapping observed with IR excitation, we also observe a long lifetime (about 1 ps) component to both the depletion of hot electrons at the bottom of the conduction band and the refilling of the BGS. This points to a BGS mediated recombination process with a ps lifetime.