Electron impact ionization of water-doped superfluid helium nanodroplets: observation of He(H(2)O)(n)(+) clusters.

Electron impact mass spectra have been recorded for helium nanodroplets containing water clusters. In addition to identification of both H(+)(H(2)O)(n) and (H(2)O)(n)(+) ions in the gas phase, additional peaks are observed which are assigned to He(H(2)O)(n)(+) clusters for up to n=27. No clusters are detected with more than one helium atom attached. The interpretation of these findings is that quenching of (H(2)O)(n)(+) by the surrounding helium can cool the cluster to the point where not only is fragmentation to H(+)(H(2)O)(m) (where m < or = n-1) avoided, but also, in some cases, a helium atom can remain attached to the cluster ion as it escapes into the gas phase. Ab initio calculations suggest that the first step after ionization is the rapid formation of distinct H(3)O(+) and OH units within the (H(2)O)(n)(+) cluster. To explain the formation and survival of He(H(2)O)(n)(+) clusters through to detection, the H(3)O(+) is assumed to be located at the surface of the cluster with a dangling O-H bond to which a single helium atom can attach via a charge-induced dipole interaction. This study suggests that, like H(+)(H(2)O)(n) ions, the preferential location for the positive charge in large (H(2)O)(n)(+) clusters is on the surface rather than as a solvated ion in the interior of the cluster.

Electron impact ionization of haloalkanes in helium nanodroplets.

Electron impact (EI) mass spectra of a selection of C1-C3 haloalkanes in helium nanodroplets have been recorded to determine if the helium solvent can significantly reduce molecular ion fragmentation. Haloalkanes were chosen for investigation because their EI mass spectra in the gas phase show extensive ion fragmentation. There is no evidence of any major softening effect in large helium droplets ( approximately 60 000 helium atoms), but some branching ratios are altered. In particular, channels requiring C-C bond fission or concerted processes leading to the ejection of hydrogen halide molecules are suppressed by helium solvation. Rapid cooling by the helium is not sufficient to account for all the differences between the helium droplet and gas phase mass spectra. It is also suggested that the formation of a solid "snowball" of helium around the molecular ion introduces a cage effect, which enhances those fragmentation channels that require minimal disruption to the helium cage for products to escape.

Soft or hard ionization of molecules in helium nanodroplets? An electron impact investigation of alcohols and ethers.

Electron impact (70 eV) mass spectra of a series of C1-C6 alcohols encased in large superfluid liquid helium nanodroplets (approximately 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(alpha)-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.