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The electronic structure of ultra-small Au clusters on thin MgO/Ag(001) filmshas been analyzed by scanning tunneling spectroscopy and density functionaltheory. The clusters exhibit two-dimensional (2D) quantum well states, whoseshapes resemble the eigen-states of a 2D electron gas confined in a parabolicpotential. From the symmetries of the HOMO and LUMO of a particular cluster,its electron filling and charge state is determined. In accordance to a DFTBader-charge analysis, aggregates containing up to twenty atoms accumulate oneto four extra electrons due to a charge transfer from the MgO/Ag interface. TheHOMO - LUMO gap is found to close for clusters containing between 70 and 100atoms.

Quantum well states in two-dimensional gold clusters on MgO thin films