The optical absorption spectra of a series of small gold clusters and their cations have been measured, between 1.9 and 5.6 eV, using a method based upon the photodepletion of a molecular beam of their van der Waals complexes containing one and two xenon atoms. This method provides size-specific information even though the molecular beam contains a wide range of cluster sizes. There is little difference between the spectra of complexes containing one or two xenon atoms. However there is a pronounced odd–even alternation in the spectra of gold clusters with differing numbers of valence s electrons. This alternation is described in terms of a simple electron pairing scheme. The spectrum for Au13 is in reasonable agreement with Dirac scattered-wave molecular orbital considerations for icosahedral Au13 [A. F. Ramos, R. Arratia-Perez, and G. L. Malli, Phys. Rev. B 35, 3790 (1987)]. This description of the molecular and electronic structure of small gold clusters in terms of localized molecular orbitals is contrasted with other models based upon jellium potentials and delocalized excitations that have been used to describe small clusters of alkali metals and silver. The bonding in gold clusters is influenced by relativistic effects that increase the degree of sd hybridization in the molecular orbitals. Even though gold clusters can be described in this way, some evidence for electron shells is also presented. Thus, it is concluded that structural motifs other than jellium potentials can lead to shell structure in cluster properties.

No abstract

We report on delayed electron emission from free tungsten clusters, excited by light from a Q-switched YAG laser. Using a novel ion extraction lens, electron emission can be analyzed over a time range of 50 ns–5 μs after the laser pulse without interference from prompt ions. All clusters of size 5≤n≤40 exhibit delayed emission on this time scale, while delayed emission from smaller clusters does not occur. We analyze the time dependence and size dependence of the emission rate for different wavelengths and fluences. The yield of delayed ions may exceed the yield of prompt ions for intermediate laser fluences. A statistical model is proposed which is based on the assumption that energy randomization in the electronically excited clusters proceeds much faster than in 50 ns, i.e., that the observed phenomenon is the (cluster) analog of thermionic emission. Good agreement with all our experimental findings is achieved, although the model invokes only one adjustable parameter. We argue that other delayed deexcitation channels, namely, emission of atoms or photons, are not significant under our experimental conditions.

No abstract