Bulk and surface electronic states of MgTi2O4 have been investigated by means of x-ray absorption spectroscopy (XAS), hard x-ray photoemission spectroscopy (HAXPES), and theoretical calculations. The Ti 2p XAS spectra exhibit multiplet structures derived from the bulk Ti3+ and surface Ti4+ features. In the surface sensitive O 1s XAS of the total electron yield mode, the magnitude of ligand field splitting is enhanced due to existence of surface Ti4+ species. The bulk-sensitive O 1s XAS spectrum taken in the total fluorescence yield mode is well reproduced by unoccupied part of O 2p density of states obtained by band structure calculations with on-site Coulomb interaction U for Ti 3d. In addition, occupied part of the calculated Ti 3d density of states agrees with the hard x-ray photoemission spectrum indicating Mottness of Ti 3d electrons. In Mg1−xFexTi2O4, the bulk sensitive Fe 2p XAS is consistent with high spin Fe2+ indicating isovalent substitution for Mg while the surface sensitive Fe 2p XAS includes high spin Fe3+. The multiplet structures in the Ti 2p and Fe 2p XAS spectra show that the 3d electrons in the bulk Ti3+ and Fe2+ are basically localized. On the other hand, a low energy shoulder of the Ti 2p HAXPES peak, which can be assigned to Ti2+ or screening effect, suggests charge fluctuation due to proximity to the metal–insulator transition.
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