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Abstract
Proton mobility in water occurs quickly according to the so-called Grotthuss mechanism. This process and its elementary reaction steps can be studied in great detail by applying suitable mass spectrometric methods to ionic water clusters. Careful choice of suitable core ions in combination with analysis of cluster size trends in hydrogen/deuterium isotope exchange rates allows for detailed insights into fascinating dynamical systems. Analysis of the experiments has been promoted by extensive and systematic quantum chemical model calculations. Detailed low-energy mechanistic pathways for efficient water rearrangement and proton transfer steps, in particular cases along short preformed "wires" of hydrogen bonds, have been identified in consistency with experimental findings.
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