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| - Enhanced Concentration of Polarizable Anions at the Liquid Water Surface: SHGSpectroscopy and MD Simulations of Sodium Thiocyanide
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| - Contrasting current textbook descriptions, a consistent picture of substantial concentration enhancement ofhighly polarizable anions at the surface of aqueous electrolyte solutions is emerging. Such enhancement mayhave important implications for chemistry occurring on aqueous aerosols and ocean surfaces. Here we presenta combined experimental and theoretical investigation of the liquid/air interface of aqueous sodium thiocyanideat varying salt concentrations. Normalized second harmonic generation intensities fitted to Langmuir isothermsyield a Gibbs free energy of adsorption of −1.80 kcal/mol. These results are in accord with molecular dynamicssimulations in slab geometry, which predict an appreciable surface enhancement of SCN-.
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