A versatile setup for studying size and charge-state selected polyanionic nanoparticles.

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., Ag800 7-. The capabilities of the setup are demonstrated by experiments extracting electronic and optical properties of polyanionic metal clusters by analyzing the corresponding photoelectron spectra.

Core-hole screening as a probe for a metal-to-nonmetal transition in lead clusters.

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.