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

Citation

Dinpajooh M., E. Biasin, E.T. Nienhuis-Marcial, S.T. Mergelsberg, C.J. Benmore, G.K. Schenter, and J.L. Fulton, et al. 2024. Detecting Underscreening and Generalized Kirkwood Transitions in Aqueous Electrolytes. Journal of Chemical Physics 161, no. 15:Art. No. 151102. PNNL-SA-189103. doi:10.1063/5.0234518

Research topics