Helium atoms bind strongly to alkali cations which, when embedded in liquid helium, form so-called snowballs. Calculations suggest that helium atoms in the first solvation layer of these snowballs form rigid structures and that their number (n) is well defined, especially for the lighter alkalis. However, experiments have so far failed to accurately determine values of n. We present high-resolution mass spectra of Na+Hen, K+Hen, Na2+Hen and K2+Hen, formed by electron ionization of doped helium droplets; the data allow for a critical comparison with several theoretical studies. For sodium and potassium monomers the spectra indicate that the value of n is slightly smaller than calculated. Na2+Hen displays two distinct anomalies at n=2 and n=6, in agreement with theory; dissociation energies derived from experiment closely track theoretical values. K2+Hen distributions are fairly featureless, which also agrees with predictions.

The submersion of sodium clusters beyond a critical size in helium nanodroplets, which has recently been predicted on theoretical grounds, is demonstrated for the first time. Confirmation of a clear transition from a surface location, which occurs for alkali atoms and small clusters, to full immersion for larger clusters, is provided by identifying the threshold electron energy required to initiate Na n cluster ionization. On the basis of these measurements, a lower limit for the cluster size required for submersion, n ≥ 21, has been determined. This finding is consistent with the recent theoretical prediction.

We report on a combined experimental and theoretical study of Li+ ions solvated by up to 50 He atoms.

Small alkali clusters do not submerge in liquid helium nanodroplets but instead survive predominantly in high spin states that reside on the surface of the nanodroplet. However, a recent theoretical prediction by Stark and Kresin [Phys. Rev. B 81, 085401 (2010)], based on a classical description of the energetics of bubble formation for a fully submerged alkali cluster, suggests that the alkali clusters can submerge on energetic grounds when they exceed a critical size. Following recent work on sodium clusters, where ion yield data from electron impact mass spectrometry was used to obtain the first experimental evidence for alkali cluster submersion, we report here on similar experiments for potassium clusters. Evidence is presented for full cluster submersion at n > 80 for K n clusters, which is in good agreement with the recent theoretical prediction. In an additional observation, we report "magic number" sizes for both K n + and K n 2+ ions derived from helium droplets, which are found to be consistent with the jellium model.

Electrons with virtually no kinetic energy (close to 0 eV) trigger the decomposition of cytotoxic cyclobutane-pyrimidine dimer (CPD) into a surprisingly large variety of fragment ions plus their neutral counterparts. The response of CPD to low energy electrons is thus comparable to that of explosives like trinitrotoluene (TNT). The dominant unimolecular reaction is the splitting into two thymine like units, which can be considered as the essential molecular step in the photolyase of CPD. We find that CPD is significantly more sensitive towards low energy electrons than its thymine building blocks. It is proposed that electron attachment at very low energy proceeds via dipole bound states, supported by the large dipole moment of the molecule (6.2 D). These states act as effective doorways to dissociative electron attachment (DEA).