Applying ZEKE-spectroscopy to clusters

In this paper we describe the application of a special form of electron photodetachment spectroscopy, zero electron kinetic energy (ZEKE) spectroscopy, to the study of cold metal cluster anions. From this study we have obtained vibrational and thus structural information of several neutral and charged clusters, e.g. Au ₂ ^?/0 , Ag ₃ ^?/0 , Sn ₂ ^?/0 and Al ₃ ^?/0 . In addition, in separate measurements of the relative photodetachment cross section of Au ₂ ^? , we have discovered sharp resonances which are due to electronic autodetachment from a short lived excited state.     

Direct observation of the dynamics of electronic excitations in molecules and small clusters

Femtosecond time-resolved photoelectron spectroscopy is applied to study relaxation paths of excited states of mass-selected negatively charged clusters. As a first example, the lifetime of an excited state of the carbon trimer anion is measured directly. In addition, the mechanism of the decay, i.e., the configurations of the participating electronic states, is determined from the photoelectron spectra. In general, this method can be used to study all kinds of electronic excitation and relaxation processes in mass-selected nanoparticles.     

Spectroscopic evidence for the tricapped trigonal prism structure of semiconductor clusters

We have obtained photoelectron spectra (PES) for silicon cluster anions with up to 20 atoms. Efficient cooling of species in the source has allowed us to resolve multiple features in the PES for all sizes studied. Spectra for an extensive set of low-energy Si(-)(n) isomers found by a global search have been simulated using density functional theory and pseudopotentials. Except for n = 12, calculations for Si(-)(n) ground states agree with the measurements. This does not hold for other plausible geometries. Hence PES data validate the tricapped trigonal prism morphologies for medium-sized Si clusters.     

Appearance of bulk properties in small tungsten oxide clusters

Contrary to the conventional understanding that atomic clusters usually differ in properties and structure from the bulk constituents of which they are comprised, we show that even a dimer of tungsten oxide (WO(3))(2) possesses bulklike features and the geometry of a small cluster containing only 4 tungsten and 12 oxygen atoms bears the hallmarks of crystalline tungsten oxide, WO(3). This observation, based on a synergistic approach involving mass distributions under quasisteady state conditions, photoelectron spectroscopy, and first principles molecular orbital theory, not only illustrates the existence of a class of strongly covalent or ionic materials whose embryonic forms are tiny clusters but also lends the possibility that a fundamental understanding of complex processes such as catalytic reactions on surfaces may be achieved on an atomic scale with clusters as model systems.