Detecting underscreening and generalized Kirkwood transitions in aqueous electrolytes
Mohammadhasan Dinpajooh, Elisa Biasin, Emily T. Nienhuis, Sebastian T. Mergelsberg, Chris J. Benmore, Gregory K. Schenter, John L. Fulton, Shawn M. Kathmann, Christopher J. Mundy
Abstract
We establish the connection between the measured small angle x-ray scattering signal and the charge-charge correlations underlying Kirkwood transitions (KTs) in 1:1, 2:1, and 3:1 aqueous electrolytes. These measurements allow us to obtain underscreening lengths for bulk electrolytes independently verified by theory and simulations. Furthermore, we generalize the concept of KTs beyond those theoretically predicted for 1:1 electrolytes, which involves the inverse screening length, a0, and the inverse periodicity length, Q0. Above the KTs, we find a universal scaling of a0∝c-ζ/3 and Q0 ∝ c1/3 for the studied electrolyte solutions, where ζ is the ionic strength factor.