Photoelectron spectra of cold (10 K) size selected water cluster anions (H(2)O)(n) (-) and (D(2)O)(n) (-) have been measured in the size range n=20-120. A new isomer with a higher binding energy than the so-called isomer I has been identified, which appears in the size range n=25-30 and for (H(2)O)(n) (-) becomes dominant at n=46. Magic numbers observed in the mass spectra of the cluster anions provide evidence that this new isomer class consists of clusters with an internal electron.

Photoelectron spectra of low temperature silicon doped gold cluster anions Au(n)Si(-) with n = 2-56 and silver cluster anions Ag(n)Si(-) with n = 5-82 have been measured. Comparing the spectra as well as the general size dependence of the electron detachment energies to the results on undoped clusters shows that the silicon atom changes the apparent free electron count in the clusters. In the case of larger gold clusters (with more than about 30 gold atoms) the silicon atom seems to consistently delocalize all of its four valence electrons, while in the case of the silver clusters a less uniform behavior is observed. Here the silicon atoms act partly as electron donors, partly as electron acceptors, without following an obvious simple principle. Additionally some structural information can be obtained from the measured spectra: while Ag(54)Si(-) seems to adopt an icosahedral structural motif, Au(54)Si(-) seems to take on a low symmetry structure, much like the corresponding pure 55 atom clusters. This indicates that for such larger clusters the incorporation of a single silicon atom does not change the ground state geometry significantly.

Oxygen-doped sodium cluster anions Na(n)O(2) (-) with n=41-148 have been studied by low temperature photoelectron spectroscopy and density functional theory (DFT), with a particular emphasis on those sizes where a spherical electron shell closing is expected. The experimental spectra are in good agreement with the electronic density of states of the DFT lowest energy structures. The cluster structures show segregation between an ionically bonded molecular unit located at the cluster surface and a metallic part. The DFT calculations reveal that each oxygen atom removes two electrons from the metallic electron gas in order to become an O(2-) dianion. A jellium model would therefore predict the electron shell closings to be shifted up by four sodium atoms with respect to pure Na(n) (-) cluster anions. The electron shell closings for Na(n)O(2) (-) are located at n=43, 61, 93, and 139, so the expected four-atom shift is observed only for the small clusters of up to n=61, while a two-atom shift is observed for the larger clusters. The DFT calculations explain this departure from jellium model predictions in terms of a structural transition in the ionically bonded molecular unit.

Photoelectron spectra of large size selected water cluster anions (H2O) n – (n = 100–1100) have been measured at a low cluster temperature (80 K). An extensive peak analysis has been conducted in order to determine average and isomer-resolved vertical detachment energies (VDE) of the hydrated electron. This allows us, in combination with the reevaluated data of the previously reported results on small- and medium-sized water cluster anions (J. Chem. Phys.2009131144303), to draw a comprehensive picture of the size-dependent development of the VDEs of water clusters. This allows for an improved extrapolation of the cluster VDEs to the bulk, which yields a value of 3.60 ± 0.03 eV. The general size dependence of the VDEs is in very good agreement with a standard dielectric model.