The electronic structure of NiO nanometric planar islands on highly oriented pyrolitic graphite has been studied by means of the Ni 2p and O 1s x-ray absorption spectra. The O 1s spectrum of the early stages of growth shows a double peak at threshold which is attributed to a splitting of the unoccupied Ni e(g) states. This spectrum is compared to previous results for 3 nm NiO nanoparticles which also show a rather similar splitting of the Ni e(g) states. This splitting observed in the O 1s spectra of the NiO nanostructures is caused by the reduced symmetry of the Ni ions at the surface. Cluster model calculations for a high-spin Ni2+ ion performed in both octahedral (bulk) and pyramidal (surface) symmetries confirm this interpretation. This new interpretation of the surface electronic structure of NiO suggests a revision of the accepted concepts concerning this system.
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