Search

Neon cluster ions Ne$_s^+$ grown in pre-ionized, mass-to-charge selected helium nanodroplets (HNDs) reveal a strong enrichment of the heavy isotope $^{22}$Ne that depends on cluster size s and the experimental conditions. For small sizes the enrichment is much larger than previously reported for bare neon clusters grown in nozzle expansions and subsequently ionized. The enrichment is traced to the massive evaporation of neon atoms in a collision cell that is used to strip helium from the HNDs. We derive a relation between the enrichment of $^{22}$Ne in the cluster ion and its corresponding depletion factor $F$ in the vapor phase. The value thus found for $F$ is in excellent agreement with a theoretical expression that relates isotopic fractionation in two-phase equilibria of atomic gases to the Debye temperature. Furthermore, the difference in zero-point energies between the two isotopes computed from F agrees reasonably well with theoretical studies of neon cluster ions that include nuclear quantum effects in the harmonic approximation. Another fitting parameter provides an estimate for the size s$_i$ of the precursor of the observed Ne$_s^+$. The value is in satisfactory agreement with the size estimated by modeling the growth of Ne$_s^+$, and with lower and upper limits deduced from other experimental data. On the other hand, neon clusters grown in neutral HNDs that are subsequently ionized by electron bombardment exhibit no statistically significant isotope enrichment at all. The finding suggests that the extent of ionization-induced dissociation of clusters embedded in HNDs is considerably smaller than for bare clusters., Comment: 14 pages, 5 figures, supplementary material

We use a novel technique to solvate silver cations in small clusters of noble gases. The technique involves formation of large, superfluid helium nanodroplets that are subsequently electron ionized, mass-selected by deflection in an electric field, and doped with silver atoms and noble gases (Ng) in pickup cells. Excess helium is then stripped from the doped nanodroplets by multiple collisions with helium gas at room temperature, producing cluster ions that contain no more than a few dozen noble gas atoms and just a few (or no) silver atoms. Under gentle stripping conditions helium atoms remain attached to the cluster ions, demonstrating their low vibrational temperature. Under harsher stripping conditions some of the heavier noble gas atoms will be evaporated as well, thus enriching stable clusters Ng$_n$Ag$_m^+$ at the expense of less stable ones. This results in local anomalies in the cluster ion abundance which is measured in a high-resolution time-of-flight mass spectrometer. Based on these data we identify specific "magic" sizes n of particularly stable ions. There is no evidence though for enhanced stability of Ng$_2$Ag$^+$, in contrast to the high stability of Ng$_2$Au$^+$ that derives from the covalent nature of the bond for heavy noble gases. "Magic" sizes are also identified for Ag$_2^+$ dimer ions complexed with He or Kr. Structural models will be tentatively proposed. A sequence of magic numbers $n$ = 12, 32, 44, indicative of three concentric solvation shells of icosahedral symmetry, is observed for He$_n$H$_2$O$^+$.

We demonstrate a novel method to ionize molecules or molecular clusters by proton transfer at temperatures below 1 K. The method yields nascent ions and largely eliminates secondary reactions, even for notoriously "delicate" molecules. Protonation is achieved inside liquid helium nanodroplets (HNDs) and begins with the formation of (H$_{2}$)$_{m}$H$^{+}$ ions as the proton donors. In a separate and subsequent step the HNDs are doped with a proton acceptor molecule, X. Proton transfer occurs between X and the cold proton donor ions inside a helium droplet, an approach that avoids the large excess energy that is released if HNDs are first doped and then ionized. Mass spectra, recorded after stripping excess helium and hydrogen in a collision cell, show that this method offers a new way to determine proton affinities of molecules and clusters by proton-transfer bracketing, to investigate astrochemically relevant ion-molecule reactions at sub-kelvin temperatures, and to prepare XH$^{+}$ ions that are suitable for messenger-tagging action spectroscopy., Comment: 9 pages, 4 figures, electronic supplementary information

Positively charged cluster ions of phosphorus were formed upon electron ionization of doped helium nanodroplets. The vapors of red phosphorus and a phosphate sample were picked up into neutral and charged helium nanodroplets. Independent on the conditions used, the cluster size distributions exhibit pronounced odd-even oscillations that are opposite to almost all experimental and theoretical patterns published in the literature. The low temperature environment of the superfluid He matrix quenches fragmentation and the charged phosphorus clusters resemble the structure of the neutral precursors., Comment: 12 pages, 6 figures

We report on the production and study of stable, highly charged droplets of superfluid helium. Using a novel experimental setup we produce neutral beams of liquid helium nanodroplets containing millions of atoms or more that can be ionized by electron impact, mass-per-charge selected, and ionized a second time before being analyzed. Droplets containing up to 55 net positive charges are identified and the appearance sizes of multiply charge droplets are determined as a function of charge state. We show that the droplets are stable on the millisecond time scale of the experiment and decay through the loss of small charged clusters, not through symmetric Coulomb explosions., Comment: 5 pages, 3 figures, published in Physical Review Letters