Valence- and inner-shell spectroscopy on rare-gas clusters

An overview of the present status of valence- and inner-shell spectroscopy on rare-gas clusters is given. Fluorescence excitation, time-of-flight ion and photoelectron spectroscopy with synchrotron excitation was used to study the electronic level structure of rare-gas clusters. Ne and Ar clusters covering the size range from the monomer up to a few thousand atoms/cluster are used as examples. Specific advantages and limitations of different methods of the study of electronic level structure as well as geometrical structure are discussed. A wealth of information on the evolution of electronic level structure has already been obtained. Nevertheless, several interesting questions concerning the evolution of energy-level shifts remain unresolved. Prospects for future work and experimental developments are given

Size and Isotope Effects of Helium Clusters and Droplets: Identification of Surface and Bulk-Volume Excitations

We report a comprehensive investigation of the electronically excited states of helium clusters and droplets of sizes ranging from a few to several 10(7) atoms using time-resolved fluorescence excitation spectroscopy and quantum chemical ab initio calculations. We employ various approaches for our analysis considering the lifetime-dependence of the fluorescence intensity, spectral shifts, intensity scaling with cluster size, isotopic dependence, and density-dependence of the calculated electron wave function radii. A unique feature of helium clusters and droplets is their radially varying particle density. Our results show that short-lived fluorescence is sensitive to regions of increased density and probes excitations located in the bulk volume, whereas long-lived fluorescence is sensitive to regions of reduced density such as for small clusters or for the surface of large droplets. Spectra of (3)He droplets serve as a reference for low density, but are free from contributions of small clusters. This allows us to distinguish regions of reduced density as these can be due to both surface states or small clusters. Our analysis reveals a picture where spectral features are related to regions of different density due to isotopic composition, cluster size, and surface or bulk volume location of the excitations. The 2s and 2p related excitations appear as blue-shifted wings for small clusters or for excited atoms within the surface layer, whereas in the bulk-volume of large droplets, they appear as distinct bands with large intensities, dominating the entire spectrum. Excitations at energies higher than 23 eV are unambiguously assigned to regions of low and medium density location within the deeper parts of the surface layer but show no relation to the bulk volume. Our findings support the idea that in liquid helium high-lying states and, in particular, Rydberg states are quenched in favor of the 2s and 2p excitations