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The solvation of alkali and halide ions in the aqueous environment has been a subject of intense experimental and theoretical research with multidisciplinary interests; yet, a comprehensive molecular-level understanding has still not been obtained. In recent years, electron spectroscopy has been increasingly applied to study the electronic and structural properties of aqueous ions with implications, especially in atmospheric chemistry. In this work, we report core and valence level (Cl 2p, Cl 3p, and K 3p) photoelectron spectra of the common alkali halide, KCl, doped in gas-phase water clusters in the size range of a few hundred water molecules. The results indicate that the electronic structure of these nanosolutions shows a distinct character from that observed at the liquid-vapor interface in liquid microjets and ambient pressure setups. Insights are provided into the unique solvation properties of ions in a nanoaqueous environment, emerging properties of bulk electrolyte solutions with growing cluster size, and sensitivity of the electronic structure to varying solvation configurations.

Electronic excitations in the valence shell of Ne clusters were studied by fluorescence spectroscopy. The measured fluorescence excitation functions contain information about the nature and number of excitonic states and the mean cluster size of the produced size distribution. Mean cluster sizes were determined by comparing surface and bulk contributions using a multidimensional fitting algorithm, with good agreement to commonly used scaling laws. The influence of different size distributions, which were not considered in previous investigations, on homogeneous noble gas cluster jets is implemented in the proposed model. The present work is the first approach using fluorescence spectroscopy for the determination of the mean size of Ne cluster jets created by supersonic expansion.