March 7, 2025
Journal Article
Detecting Underscreening and Generalized Kirkwood Transitions in Aqueous Electrolytes
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, $a_0$ and the inverse periodicity length, $Q_0$. Above the KTs, we find a universal scaling of $a_0 \propto c^{-\sqrt{\zeta}/3}$ and $Q_0 \propto c^{1/3}$ for the studied electrolyte solutions, where $\zeta$ is the ionic strength factor.Published: March 7, 2025