• clusters;
  • helium;
  • hydrides;
  • ion–molecule reactions;
  • mass spectrometry


High-resolution mass spectra of helium nanodroplets doped with hydrogen or deuterium reveal that copious amounts of helium can be bound to H+, H2+, H3+, and larger hydrogen-cluster ions. All conceivable HenHx+ stoichiometries are identified if their mass is below the limit of ≈120 u set by the resolution of the spectrometer. Anomalies in the ion yields of HenHx+ for x=1, 2, or 3, and n≤30 reveal particularly stable cluster ions. Our results for HenH1+ are consistent with conclusions drawn from previous experimental and theoretical studies which were limited to smaller cluster ions. The HenH3+ series exhibits a pronounced anomaly at n=12 which was outside the reliable range of earlier experiments. Contrary to findings reported for other diatomic dopant molecules, the monomer ion (i.e. H2+) retains helium with much greater efficiency than hydrogen-cluster ions.