Valence band photoemission spectra (PES) for both bulk and nanocrystal CeO2 have been measured on and off resonance of Ce 4d-4f absorption edge. The PES show that the bulk and nanocrystal CeO2 of diameter ranging from 8nm to 50nm exhibit a peak near Fermi edge with binding energy of about 1.8eV. The 1.8eV peak shows a strong dependence on excitation energy, although it looks like the contribution of Ce3+ ion following the data reported in literatures. However, according to the results of resonance photoemission and X-ray absorption spectra at 1s edge, this electronic structure may be associated to the intermediate state charge transfer effects.
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