There is Nothing Anomalous about 'Anomalous' Underscreening in Concentrated Electrolytes

Abstract

Over the last decade, experimental measurements of electrostatic screening lengths in concentrated electrolytes have exceeded theoretical predictions by orders of magnitude. This disagreement has led to a paradigm in which such screening lengths are referred to as 'anomalous underscreening', while others - predominantly those predicted by theory and molecular simulation - are referred to as 'normal underscreening'. Herein we use discrete Fourier analysis of the radial charge density obtained from molecular dynamics simulations to reveal the origin of anomalous underscreening in concentrated electrolytes. Normal underscreening above the Kirkwood point arises from low-frequency decay modes of the electrostatic potential, while anomalous underscreening arises from high-frequency decay modes that are observed only at high concentrations. The screening length associated with a particular decay mode is in turn determined by the degree of short-range interference between ion-ion correlation functions. The long-range decay associated with anomalous underscreening is thus ultimately determined by short range structure in the bulk electrolyte. These results reconcile the disagreement between experimental measurements and theoretical predictions of screening lengths in concentrated electrolytes.