Size and Origins of Long-Range Orientational Water Correlations in Dilute Aqueous Salt Solutions.

Long-range ordering of water around solutes has been repeatedly invoked as the key to its biological function. Recently, it has been shown that in an 8 mM aqueous NaCl solution the orientational correlation between water molecules extends beyond 8 nm. This was interpreted as arising from ion-induced long-range effects on the water collective hydrogen-bond interactions. Each ion was suggested to affect >10 000 water molecules, leading to a picture involving nanoscopic "ordered domains". Using molecular dynamics simulations, we show that the very small long-range tail in the correlation function is caused primarily by pairs of water molecules belonging to different ions' hydration shells and can be made to practically disappear by rearranging the ionic positions. This means that the ion-induced water orientational ordering in millimolar salt solutions cannot be separated from ion-ion interaction effects, for which the Debye-Hückel screening length shrinks to less than 1 nm at physiological ionic strengths.