Metal clusters serve as model systems to study basic problems of electronic correlation. Vacuum ultraviolet light from the free-electron laser FLASH ionizes 5d electrons from mass-separated negatively charged clusters, thus transiently leading to core-ionized neutral systems. Shielding of the core hole affects the electron binding energy. From the strong deviation from expectations of the metallic droplet and jellium models we conclude on reduced electronic shielding once the cluster size falls below about 20 atoms. This suggests a metal-to-nonmetal transition, in agreement with previous local density approximation calculations.

4f core level photoelectron spectroscopy has been performed on negatively charged lead clusters, in the size range of 10-90 atoms. We deploy 4.7 nm radiation from the free-electron laser FLASH, yielding sufficiently high photon flux to investigate mass-selected systems in a beam. A new photoelectron detection system based on a hemispherical spectrometer and a time-resolving delayline detector makes it possible to assign electron signals to each micropulse of FLASH. The resulting 4f binding energies show good agreement with the metallic sphere model, giving evidence for a fast screening of the 4f core holes. By comparing the present work with previous 5d and valence region data, 2 the paper presents a comprehensive overview of the energetics of lead clusters, from atoms to bulk. Special care is taken to discuss the differences of the valenceand core-level anion cluster photoionizations. Whereas in the valence case the escaping photoelectron interacts with a neutral system near its ground state, core-level ionization leads to transiently highly excited neutral clusters. Thus, the photoelectron signal might carry information on the relaxation dynamics.

Using the example of metal clusters, an experimental setup and procedure is presented, which allows for the generation of size and charge-state selected polyanions from monoanions in a molecular beam. As a characteristic feature of this modular setup, the further charging process via sequential electron attachment within a three-state digital trap takes place after mass-selection. In contrast to other approaches, the rf-based concept permits access to heavy particles. The procedure is highly flexible with respect to the preparation process and potentially suitable for a wide variety of anionic species. By adjusting the storage conditions, i.e., the radio frequency, to the change in the mass-to-charge ratio, we succeeded in producing clusters in highly negative charge states, i.e., [Formula: see text]. The capabilities of the setup are demonstrated by experiments extracting electronic and optical properties of polyanionic metal clusters by analyzing the corresponding photoelectron spectra.

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