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Nitrogen-doped titanium dioxide (N-TiO2), a photocatalytic material active in visible light, has been investigated by a combined experimental and theoretical approach. The material contains single-atom nitrogen impurities that form either diamagnetic (Nb-) or paramagnetic (Nb*) bulk centers. Both types of Nb centers give rise to localized states in the band gap of the oxide. The relative abundance of these species depends on the oxidation state of the solid, as, upon reduction, electron transfer from Ti3+ ions to Nb* results in the formation of Ti4+ and Nb-. EPR spectra measured under irradiation show that Nb centers are responsible for visible light absorption with promotion of electrons from the band gap localized states to the conduction band or to surface-adsorbed electron scavengers. These results provide a characterization of the electronic states associated with N impurities in TiO2 and, for the first time, a picture of the processes occurring in the solid under irradiation with visible light.

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Fs +(H) color centers at the surface of MgO have been studied using a combined EPR and quantum chemical approach. Fs +(H) are paramagnetic excess electrons centers where the unpaired electron is trapped in a surface anion vacancy. They are formed at the surface of thoroughly dehydrated MgO (1073K) upon UV irradiation under hydrogen in parallel with the formation of minor fractions of different color centers. The whole EPR spectrum resulting from irradiation has been analyzed by simulation of the experimental profile. Fs +(H) centers are characterized by an axial g tensor and display a hyperfine interaction with a hydrogen nucleus (belonging to an hydroxyl group stabilized nearby the vacancy) and two distinct families of 25Mg nuclei characterized by a large (10.5 G) and a small (0.7 G) hyperfine coupling constant, respectively. Both EPR and ab initio calculations on clusters of ions converge in indicating that the features of the centers are due to the polarization of the electron density by the positive charge of the hydrogen in the OH group toward two (or possibly three) equivalent magnesium ions of the vacancy close to the OH group itself. The formation mechanism of the centers is strictly analogous to that occurring upon contact of low ionization energy metals with the surface of MgO leading to the formation of another type of color centers. Partially hydrated MgO samples also give rise to another family of paramagnetic center based on electrons trapped in anion vacancies. This finding indicates that the structure of the partially hydroxylated oxide and the mechanism of its dehydration are still open questions.