Helium droplets provide an exotic and unique environment for the study of physical and chemical phenomena. Properties of these droplets include a low temperature (0.37 K), their superfluidity, and the ability to easily add a wide variety of atoms and molecules. This tutorial review provides a concise account of the basic principles of helium droplets, including how to form, dope, and interrogate these objects. There then follows a series of selected applications grouped under particular themes, with strong bias towards topics likely to be of particular interest to chemists.

Direct preparation of long one-dimensional (1D) nanostructures with diameters <10 nm inside superfluid helium droplets is reported. Unlike conventional chemical synthetic techniques, where stabilizers, templates, or external fields are often required to induce 1D growth, here, we exploit the use of quantized vortices to guide the formation of ultrathin nanowires. A variety of elements have been added to the droplets to demonstrate that this is a general phenomenon, including Ni, Cr, Au, and Si. Control of the length and diameter of the nanowires is also demonstrated.

A theoretical model has been developed to describe the probability of charge transfer from helium cations to dopant molecules inside helium nanodroplets following electron-impact ionization. The location of the initial charge site inside helium nanodroplets subject to electron impact has been investigated and is found to play an important role in understanding the ionization of dopants inside helium droplets. The model is consistent with a charge migration process in small helium droplets that is strongly directed by intermolecular forces originating from the dopant, whereas for large droplets (tens of thousands of helium atoms and larger) the charge migration increasingly takes on the character of a random walk. This suggests a clear droplet size limit for the use of electron-impact mass spectrometry for detecting molecules in helium droplets.

Helium droplets are large helium clusters that are capable of picking up individual atoms and molecules and show promise as nano-reactors for the synthesis of unique nanoparticles. In particular, the sequential addition of materials of different types offers opportunities for the fabrication of novel core–shell nanoparticles that cannot be synthesised by other methods. To exploit this potential, here we have carried out a mass spectrometry investigation on metal clusters in order to establish how to control the doping conditions for the fabrication of nanoparticles in superfluid helium droplets, and in particular to develop a recipe to control core and shell ratios in the case of core–shell nanoparticles. Several types of metal nanoparticles, including pure Ag, Au and Ni nanoparticles, and Ag/Au and Ni/Au core–shell systems, have been synthesised and then removed from the helium droplets by deposition on substrates for ex situ investigations using high-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The TEM imaging has been used to estimate the sizes of nanoparticles, which show a bi-model distribution under the conditions employed. We also present the first evidence that crystalline metal nanoparticles are formed by self-assembly of metal atoms in helium droplets. The XPS investigation of Ni/Au core–shell nanoparticles shows an absence of any Au 4f core-level shift that would occur on alloying of Au and Ni, which provides the first direct evidence for the successful formation of core–shell nanoparticles using superfluid helium droplets.

Electron impact (70 eV) mass spectra of a series of C₁–C₆ alcohols encased in large superfluid liquid helium nanodroplets (∼60 000 helium atoms) have been recorded. The presence of helium alters the fragmentation patterns when compared with the gas phase, with some ion product channels being more strongly affected than others, most notably cleavage of the C_α–H bond in the parent ion to form the corresponding oxonium ion. Parent ion intensities are also enhanced by the helium, but only for the two cyclic alcohols studied, cyclopentanol and cyclohexanol, is this effect large enough to transform the parent ion from a minor product (in the gas phase) into the most abundant ion in the helium droplet experiments. To demonstrate that these findings are not unique to alcohols, we have also investigated several ethers. The results obtained for both alcohols and ethers are difficult to explain solely by rapid cooling of the excited parent ions by the surrounding superfluid helium, although this undoubtedly takes place. A second factor also seems to be involved, a cage effect which favors hydrogen atom loss over other fragmentation channels. The set of molecules explored in this work suggest that electron impact ionization of doped helium nanodroplets does not provide a sufficiently large softening effect to be useful in analytical mass spectrometry.