Anomalous Underscreening in the Restricted Primitive Model

Abstract

Underscreening is a collective term for charge correlations in electrolytes decaying slower than the Debye length. Anomalous underscreening refers to phenomenology that cannot be attributed alone to steric interactions. Experiments with concentrated electrolytes and ionic fluids report anomalous underscreening, which so far has not been observed in simulation. We present Molecular Dynamics simulation results exhibiting anomalous underscreening that can be connected to cluster formation. A theory that accounts for ion pairing confirms the trend. Our results challenge the classic understanding of dense electrolytes impacting the design of technologies for energy storage and conversion.

References in corpus (8)

• The Electrostatic Screening Length in Concentrated Electrolytes Increases with Concentration
• Scaling analysis of the screening length in concentrated electrolytes
• Density functional theory for hard-sphere mixtures: the White-Bear version Mark II
• Underscreening in concentrated electrolytes
• Primitive Model Electrolytes in the Near and Far Field: Decay Lengths from DFT and Simulations
• The Primitive Model in Classical Density Functional Theory: Beyond the Standard Mean-Field Approximation
• Bayesian unsupervised learning reveals hidden structure in concentrated electrolytes
• Underscreening and hidden ion structures in large scale simulations of concentrated electrolytes

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• Magnetic Interactions between Nanoscale Domains in Correlated Liquids
• Exceptionally strong double-layer barriers generated by polyampholyte salt
• Length scales in electrolytes
• Bridging Electrostatic Screening and Ion Transport in Lithium Salt-Doped Ionic Liquids
• Structural and Dynamical Crossovers in Dense Electrolytes
• Mutual effect of charge- and number-density correlations in ionic liquids and concentrated electrolytes
• On the electrical double layer capacitance of the restricted primitive model: a link between the mesoscopic theory and the associative mean spherical approximation
• Temperature-Gradient Effects on Electric Double Layer Screening in Electrolytes
• Polyampholyte model of ion clusters: double-layer interactions in the presence of dissociated simple salt