Nanometer-Scale Correlations in Aqueous Salt Solutions

J Phys Chem Lett. 2020 Apr 2;11(7):2598-2604. doi: 10.1021/acs.jpclett.0c00322. Epub 2020 Mar 18.

Abstract

The intermediate-range (1-4 nm) correlation of cations, anions, and water in aqueous alkaline earth salt solutions is measured using synchrotron X-ray diffraction. We differentiate from the entire solution structure factor, SX(Q), a separate region at low Q (<1.5 Å-1) containing local diffraction maxima (prepeaks) that indicate nanometer-scale oscillatory behavior. These features are quantitatively reproduced with classical molecular dynamics simulations. At high concentrations, the prepeaks emerge from correlations arising from the existence of small quasi close-packed lattice-like structures comprised of cation hydration spheres. We also analyze the concentration dependence of the prepeak and discuss the overall results in light of the rich literature dealing with intermediate-range correlations underlying universal phenomena in concentrated electrolytes.