Screening Lengths in Ionic Fluids

Abstract

The decay of correlations in ionic fluids is a classical problem in soft matter physics that underpins applications ranging from controlling colloidal self-assembly to batteries and supercapacitors. The conventional wisdom, based on analyzing a solvent-free electrolyte model, suggests that all correlation functions between species decay with a common decay length in the asymptotic far field limit. Nonetheless, a solvent is present in many electrolyte systems. We show using an analytical theory and molecular dynamics simulations that multiple decay lengths can coexist in the asymptotic limit as well as at intermediate distances once a hard sphere solvent is considered. Our analysis provides an explanation for the recently observed discontinuous change in the structural force across a thin film of ionic liquid-solvent mixtures as the composition is varied, as well as reframes recent debates in the literature about the screening length in concentrated electrolytes.

References in corpus (12)

• Electrostatic correlations: from Plasma to Biology
• 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
• A model colloidal fluid with competing interactions: bulk and interfacial properties
• Switching the structural force in ionic liquid-solvent mixtures by varying composition
• Interfacial ordering and accompanying divergent capacitance at ionic liquid-metal interfaces
• Free energies, vacancy concentrations and density distribution anisotropies in hard--sphere crystals: A combined density functional and simulation study
• Experimental observation of structural crossover in binary mixtures of colloidal hard spheres
• Direct Observation in 3d of Structural Crossover in Binary Hard Sphere Mixtures
• Effective Electrostatic Interactions in Colloid-Nanoparticle Mixtures
• Effective interactions in the colloidal suspensions from HNC theory

Cited by in corpus (20)

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• The Primitive Model in Classical Density Functional Theory: Beyond the Standard Mean-Field Approximation
• Bayesian unsupervised learning reveals hidden structure in concentrated electrolytes
• Overscreening and Underscreening in Solid-Electrolyte Grain Boundary Space-Charge Layers
• Electric-field-induced oscillations in ionic fluids: a unified formulation of modified Poisson-Nernst-Planck models and its relevance to correlation function analysis
• Reversible heat production during electric double layer buildup depends sensitively on the electrolyte and its reservoir
• Cluster Formation induced by local dielectric saturation in Restricted Primitive Model Electrolytes
• Solvent-induced ion clusters generate long-ranged double-layer forces at high ionic strengths
• Forces between Silica Particles in Isopropanol Solutions of 1:1 Electrolytes
• Ionically charged topological defects in nematic fluids
• Length scales in electrolytes
• Exceptionally strong double-layer barriers generated by polyampholyte salt
• Bridging Electrostatic Screening and Ion Transport in Lithium Salt-Doped Ionic Liquids
• Mutual effect of charge- and number-density correlations in ionic liquids and concentrated electrolytes
• Structural and Dynamical Crossovers in Dense Electrolytes
• Polyampholyte model of ion clusters: double-layer interactions in the presence of dissociated simple salt
• Non-electrostatic interactions as random fields in charged liquids