Journal of the American Chemical Society · 2010 · 147 citations · 21 references
Natural SciencesChemistryInorganic ChemistryPhysical ChemistrySpectroscopyAquatic ChemistryHydration EffectsInfrared SpectroscopyMolecular SymmetryWater ChemistryBulk Water EffectsMolecular PhotodissociationPhotodissociation ProcessesPhotodissociation SpectroscopySulfate Chemistry
The chemical origins of the Hofmeister series are investigated using infrared photodissociation (IRPD) spectroscopy. IRPD spectra of SO(4)(2-)(H(2)O)(n) with up to 80 water molecules have a band at approximately 3710 cm(-1) for n > 43 but not for n < or = 43. This band corresponds to outer-shell water molecules with "free" OH groups similar to those at the surface of bulk water. These results indicate that the sulfate dianion has a long-range effect on water structure, and this effect is likely to be an important factor in its Hofmeister behavior.
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Negligible Effect of Ions on the Hydrogen-Bond Structure in Liquid Water
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