Solvation of Silver Ions in Noble Gases He, Ne, Ar, Kr, and Xe

J Phys Chem A. 2019 Dec 5;123(48):10426-10436. doi: 10.1021/acs.jpca.9b09496. Epub 2019 Nov 21.

Abstract

We use a novel technique to solvate silver cations in small clusters of noble gases. The technique involves the 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 of NgnAgm+ 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. On the basis of these data, we identify specific "magic" sizes n of particularly stable ions. There is no evidence, however, for enhanced stability of Ng2Ag+, in contrast to the high stability of Ng2Au+ that derives from the covalent nature of the bond for heavy noble gases. "Magic" sizes are also identified for Ag2+ dimer ions complexed with He or Kr. Structural models will be tentatively proposed. A sequence of magic numbers n = 12, 32, and 44, indicative of three concentric solvation shells of icosahedral symmetry, is observed for HenH2O+.