Underscreening and hidden ion structures in large scale simulations of concentrated electrolytes

TL;DR

This study uses Brownian Dynamics simulations to investigate ion correlations and structures in concentrated electrolytes, revealing ion clustering and non-electrostatic oscillations that explain the underscreening phenomenon observed experimentally.

Contribution

It introduces a detailed simulation analysis of ion correlations and structures in concentrated electrolytes, highlighting the role of excluded volume and ion clustering in underscreening.

Findings

Charge-charge correlation decay deviates from Debye-Hückel predictions at high concentrations.

Large-scale ion structures and like-charge ion clusters form at high concentrations.

Oscillation periods in charge correlations are dominated by excluded volume interactions.

Abstract

The electrostatic screening length predicted by Debye-H\"uckel theory decreases with increasing ionic strength, but recent experiments have found that the screening length can instead increase in concentrated electrolytes. This phenomenon, referred to as underscreening, is believed to result from ion-ion correlations and short-range forces such as excluded volume interactions among ions. We use Brownian Dynamics to simulate a version of the Restrictive Primitive Model for electrolytes over a wide range of ion concentrations, ionic strengths, and ion excluded volume radii for binary electrolytes. We measure the decay of the charge-charge correlation among ions in the bulk, and compare it against scaling trends found experimentally and determined in certain weak coupling theories of ion-ion correlation. Moreover, we find that additional large scale ion structures emerge at high concentrations. In this regime, the frequency of oscillations computed from the charge-charge correlation function is not dominated by electrostatic interactions but rather by excluded volume interactions and with oscillation periods on the order of the ion diameter. We also find that the nearest neighbor correlation of ions sharing the same charge transitions from negative at small concentrations to positive at high concentrations, representing the formation of small, like-charge ion clusters. We conclude that the increase in local charge density due to the formation of these clusters and the topological constraints of macroscopic charged surfaces can help explain the degree of underscreening observed experimentally.