Chemistry of Transient Species in Water Clusters

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Electron induced reactions in aqueous solution contribute directly and indirectly to a multitude of chemical processes, ranging from organic synthesis via photochemical water splitting on metal electrodes to corrosion of metallic structures. Short lived intermediates of these reactions can be stabilized in water clusters. Individual reaction steps can be studied in the collision of a water cluster, in which the charged intermediate is solvated, with a neutral reaction partner in a mass spectrometer. Fundamental insight into electron induced bond cleavage in aqueous solution is expected from the reactions of hydrated electrons with gaseous hydrogen chloride. Electron induced bond cleavage in biomolecules is relevant for life sciences. Triethyl phosphate serves as a model system for the DNA backbone, its stability against electron induced reactions in aqueous solution is subject to a planned experiment. The influence of ring strain on the theoretically predicted electron induced ring opening of organic molecules is investigated with a series of saturated cyclic hydrocarbons, featuring three- to six-membered rings. Electrons may also be provided by a reactive metal center, like a monovalent transition metal ion. With these systems, various types of reactions are going to be investigated. Halogenated hydrocarbons undergo cleavage of the halogen-carbon bond upon collision with a hydrated electron. The corresponding reactions with hydrated transition metal ions are supposed to reveal the influence of the precipitation of the metal halogenide on the reaction path. Reduction of organic molecules by electron transfer is another example which will be studied in the reaction of acetonitrile with monovalent hydrated transition metal ions. Sulfur containing molecules like methyl mercaptane or dimethyl disulfide are able to form metal-sulfur bonds in addition to electron induced bond cleavage. The investigation of these reactions adds an additional degree of complexity to the experiments.