In this work, we present an alternative to complex laser setups or synchrotron light sources to accurately measure the ionization potentials of metal clusters. The setup is based on a commercial Xe flash lamp, combined with a vacuum monochromator, and has been applied to determine the ionization potentials of Sn_n clusters with n = 8–12 atoms.

The uncertainty in the determination of the ionization potentials is mainly caused by the bandwidth of the monochromator. The adiabatic ionization potentials (AIPs) are extracted from experimental photoionization efficiency curves. Franck–Condon simulations are additionally used to interpret the shape and onset of the photo-ion yield. The obtained AIPs are (all energies are in eV) Sn₈ (6.53 ± 0.05), Sn₉ (6.69 ± 0.04), Sn₁₀ (6.93 ± 0.03), Sn₁₁ (6.34 ± 0.05), and Sn₁₂ (IsoI 6.64 ± 0.04 and IsoIII 6.36 ± 0.05). Furthermore, the impact of multiple isomers present in the experiment on the photo-ion yield is addressed and compared with other experimental data in the literature.

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We present a comprehensive investigation of the dielectric behavior and geometric structures of cold neutral Si_N clusters of intermediate size with N = 12–30 atoms. For this, cryogenic electric beam deflection experiments were carried out for the first time for Si clusters at nozzle temperatures below 30 K.

In combination with quantum chemical calculations based on density functional theory and classical trajectory simulations of the rotational dynamics in the electric field, the geometric structures of the clusters are discriminated. Clusters with N < 15 favor a single-capped square antiprism as a nucleus for cluster growth, forming compact geometries in the molecular beam. Starting with 15 atoms, a prolate-like growth is observed. The prolate structures are based on stable building blocks which reappear for numerous sizes throughout the cluster growth. Finally, the transition from prolate to quasi-spherical shapes is shown to take place around Si₂₉/Si₃₀ as predicted theoretically by the literature. The influence of the exchange–correlation functional on the predicted structure and dielectric properties is discussed in detail for some clusters. Relaxation of the electric-dipole moment and therefore quenching of the observed electric response due to vibrational excitation and collisions with the background gas are also considered, which explains deviations between experiment and theory.

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