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Ionization threshold energies of Al$_n$ (n=32-95) nanoclusters are determinedby laser ionization of free neutral metal clusters thermalized to severaltemperatures in the range from 65 K to 230 K. The photoion yield curves of coldclusters follow a quadratic energy dependence above threshold, in agreementwith the Fowler law of surface photoemission. Accurate data collection andanalysis procedures make it possible to resolve very small (few parts in athousand) temperature-induced shifts in the ionization energies. Extrapolationof the data to the bulk limit enables a determination of the thermal shift ofthe polycrystalline metal work function, found to be in excellent agreementwith theoretical prediction based on the influence of thermal expansion. Smallclusters display somewhat larger thermal shifts, reflecting their greatersusceptibility to thermal expansion. Ionization studies of free size-resolvednanoclusters facilitate understanding of the interplay of surface, electronic,and lattice properties under contamination-free conditions.

Nanocluster ionization energies and work function of aluminum, and their temperature dependence