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Various aspects of molecular solvation are reviewed from the perspective provided by gas-phase aromatic solute-(solvent)n clusters. Particular emphasis is placed on hydrogen-bonded clusters, varying from 1:1 aromatic-H2O complexes up to clusters containing several water or methanol molecules. Recent advances in experimental methods for obtaining accurate structures, binding energies, and intermolecular and intramolecular vibrational spectra are highlighted. Many of these methods provide size and conformation selectivity and can be readily extended to both ground and electronically excited neutral states. The π hydrogen bond, hydrogen bonding to aromatic alcohols, water complexation to indole and its derivatives, and the hydrogen-bonded networks of benzene-(H2O)n and benzene-(CH3OH)n clusters are reviewed in special detail.
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