Competitive ion-dipole, ion-water, and water-water interactions were investigated at the molecular level in M+ (CH3CN)n(H2O)m cluster ions for M = Na and K. Different [n,m] combinations for two different n + m cluster sizes were characterized with infrared predissociation spectroscopy in the O-H stretch region and MP2 calculations. In all cases, no differences were observed between the two alkali metal ions. The results showed that at the n + m = 4 cluster size, the solvent molecules interact only with the ion, and that the interaction between the ion and the large dipole moment of CH3CN decreases the ion-water electrostatic interactions. At the n + m = 5 cluster size, at least two different hydrogen-bonded structures were identified. In these structures, the ion-dipole interaction weakens the ability of the ion to polarize the hydrogen bonds and thus decreases the strength of the water-water interactions in the immediate vicinity of the alkali metal ion.
[Show abstract][Hide abstract] ABSTRACT: Studying metal ion solvation, especially hydration, in the gas phase has developed into a field that is dominated by a tight interaction between experiment and theory. Since the studied species carry charge, mass spectrometry is an indispensable tool in all experiments. Whereas gas-phase coordination chemistry and reactions of bare metal ions are reasonably well understood, systems containing a larger number of solvent molecules are still difficult to understand. This review focuses on the rich chemistry of hydrated metal ions in the gas phase, covering coordination chemistry, charge separation in multiply charged systems, as well as intracluster and ion-molecule reactions. Key ideas of metal ion solvation in the gas phase are illustrated with rare-gas solvated metal ions.
Mass Spectrometry Reviews 07/2007; 26(4):517-41. DOI:10.1002/mas.20135 · 7.71 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The competitive solvation of the potassium ion by benzene and water is investigated at
molecular level by means of Molecular Dynamics simulations on the
(n = 1–4; m = 1–6) ionic aggregates. The preference of
K+ to bind C6H6 or H2O is investigated in
the range of temperatures in which isomerisation processes are likely by adding water and
benzene to the K+-(C6H6)n
Hydrogen bonds and the π-hydrogen bond, in spite of their weakness with
respect to the K+-π and K+-H2O
interactions, play an important role in stabilising different isomers, thus favouring
isomerisation processes. Accordingly with experimental information it has been found that
K+ bind preferably C6H6 rather than H2O and
that the fragmentation of C6H6 is only observed for aggregates
containing four molecules of benzene.
The European Physical Journal D 04/2013; 67(4). DOI:10.1140/epjd/e2013-30753-x · 1.23 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Studies of gas phase M 1 (L) n cluster ions (where M is a metal atom and L is a ligand molecule) assist our understanding of solvation and chemical processes that involve metal ions. The recent development of pulsed, tuneable OPO (optical parametric oscillator) sources capable of generating infrared light at frequencies between 1000 and 4000 cm À1 has allowed the vibrational spectra of many species to be assigned for the first time. This perspective reviews infrared spectroscopy of metal-containing cluster ions to date and discusses future opportunities.
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