Cooperativity in Ion Hydration

Abstract

Despite prolonged scientific efforts to unravel the effects of ions on the structure and dynamics of water, many open questions remain, in particular concerning the spatial extent of this effect (i.e., the number of water molecules affected) and the origin of ion-specific effects. A combined terahertz and femtosecond infrared spectroscopic study of water dynamics around different ions (specifically magnesium, lithium, sodium, and cesium cations, as well as sulfate, chloride, iodide, and perchlorate anions) reveals that the effect of ions and counterions on water can be strongly interdependent and nonadditive, and in certain cases extends well beyond the first solvation shell of water molecules directly surrounding the ion.