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 the charge state. We show that the droplets are stable on the millisecond timescale of the experiment and decay through the loss of small charged clusters, not through symmetric Coulomb explosions.

The demand for nanoscale materials of ultra-high purity and narrow size distribution is addressed. Clusters of Au, C₆₀, H₂O, and serine are produced inside helium nanodroplets using a combination of ionization, mass filtering, collisions with atomic or molecular vapor, and electrostatic extraction, in a specific and novel sequence. The helium droplets are produced in an expansion of cold helium gas through a nozzle into vacuum. The droplets are ionized by electron bombardment and subjected to a mass filter. The ionic and mass-selected helium droplets are then guided through a vacuum chamber filled with atomic or molecular vapor where they collide and “pick up” the vapor. The dopants then agglomerate inside the helium droplets around charge centers to singly charged clusters. Evaporation of the helium droplets is induced by collisions in a helium-filled radio frequency (RF)-hexapole, which liberates the cluster ions from the host droplets. The clusters are analyzed with a time-of-flight mass spectrometer. It is demonstrated that using this sequence, the size distribution of the dopant cluster ions is distinctly narrower compared to ionization after pickup. Likewise, the ion cluster beam is more intense. The mass spectra show, as well, that ion clusters of the dopants can be produced with only few helium atoms attached, which will be important for messenger spectroscopy. All these findings are important for the scientific research of clusters and nanoscale materials in general.

In the present work we observe that helium nanodroplets colliding with surfaces can exhibit splashing in a way that is analogous to classical liquids. We use transmission electron microscopy and mass spectrometry to demonstrate that neutral and ionic dopants embedded in the droplets are efficiently backscattered in such events. High abundances of weakly bound He-tagged ions of both polarities indicate a gentle extraction mechanism of these ions from the droplets upon collision with a solid surface. This backscattering process is observed for dopant particles with masses up to 400 kilodaltons, indicating an unexpected mechanism that effectively lowers deposition rates of nanoparticles formed in helium droplets.

Helium droplets represent a cold inert matrix, free of walls with outstanding properties to grow complexes and clusters at conditions that are perfect to simulate cold and dense regions of the interstellar medium. At sub‐Kelvin temperatures, barrierless reactions triggered by radicals or ions have been observed and studied by optical spectroscopy and mass spectrometry. The present review summarizes developments of experimental techniques and methods and recent results they enabled.

Helium tagging in action spectroscopy is an efficient method for measuring the absorption spectra of complex molecular ions with minimal perturbations to the gas phase spectra. We have used superfluid helium nanodroplets doped with corannulene to prepare cations of these molecules complexed with different numbers of He atoms. In total we identify 13 different absorption bands from corannulene cations between 5500 Å and 6000 Å. The He atoms cause a small, chemically induced redshift of the band positions of the corannulene ion. By studying this effect as a function of the number of solvating atoms we are able to identify the formation of solvation structures that are not visible in the mass spectrum. The solvation features detected using action spectroscopy agree very well with the results of atomistic modeling based on path-integral molecular dynamics simulations. By additionally doping our He droplets with D₂, we produce protonated corannulene ions. The absorption spectrum of these ions differs significantly from the case of the radical cations as the numerous narrow bands are replaced by a broad absorption feature that spans nearly 2000 Å in width.

The detection of multiply charged helium droplet anions is reported for the first time. By ionizing droplets of superfluid helium with low energy electrons (up to 25 eV), it was possible to produce droplets containing up to five negative charges, which remain intact on the timescale of the experiment. The appearance sizes for different charge states are determined and are found to be orders of magnitude larger than for the equivalent cationic droplets, starting at 4 million He atoms for dianions. Droplets with He*⁻ as charge carriers show signs of being metastable, but this effect is quenched by the pickup of water molecules.