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Screening of a strongly charged macroion by multivalent counterions is considered. It is shown that counterions form a strongly correlated liquid at the surface of the macroion. Cohesive energy of this liquid leads to additional attraction…

Soft Condensed Matter · Physics 2009-10-31 B. I. Shklovskii

We perform computational investigations of electrolyte-mediated interactions of charged colloidal particles confined within nanochannels. We investigate the role of discrete ion effects, valence, and electrolyte strength on colloid-wall…

Soft Condensed Matter · Physics 2023-02-28 Inderbir S. Sidhu , Amalie L. Frischknecht , Paul J. Atzberger

We present an exact field-theoretic formulation for a fluctuating, generally asymmetric, salt density in the presence of a charged plate. The non-linear Poisson-Boltzmann equation is obtained as the saddle-point of our field theory action.…

Soft Condensed Matter · Physics 2007-05-23 William Kung , A. W. C. Lau

Electrophoretic (EP) mobility reversal is commonly observed for strongly charged macromolecules in multivalent salt solutions. This curious effect takes place, e.g., when a charged polymer, such as DNA, adsorbs excess counterions so that…

Soft Condensed Matter · Physics 2023-03-28 Xiang Yang , Sahin Buyukdagli , Alberto Scacchi , Maria Sammalkorpi , Tapio Ala-Nissila

A variational theory is developed to study electrolyte solutions, composed of interacting point-like ions in a solvent, in the presence of dielectric discontinuities and charges at the boundaries. Three important and non-linear…

Soft Condensed Matter · Physics 2013-05-29 Sahin Buyukdagli , Manoel Manghi , John Palmeri

The description of a conducting medium in thermal equilibrium, such as an electrolyte solution or a plasma, involves nonlinear electrostatics, a subject rarely discussed in the standard electricity and magnetism textbooks. We consider in…

Chemical Physics · Physics 2018-08-01 C. G. Gray , P. J. Stiles

Understanding the response of the surface of metallic solids to external electric field sources is crucial to characterize electrode-electrolyte interfaces. Continuum electrostatics offer a simple description of the induced charge density…

Chemical Physics · Physics 2021-12-14 Giovanni Pireddu , Laura Scalfi , Benjamin Rotenberg

In the present work, we study an electrolyte solution confined between planar surfaces with nonopatterned charged domains, which has been connected to a bulk ionic reservoir. The system is investigated through an improved Monte Carlo (MC)…

Soft Condensed Matter · Physics 2020-09-29 Amin Bakhshandeh , Maximiliano Segala , Thiago Colla

The classical Poisson-Boltzmann (PB) theory of electrolytes assumes a dilute solution of point charges with mean-field electrostatic forces. Even for very dilute solutions, however, it predicts absurdly large ion concentrations (exceeding…

Chemical Physics · Physics 2007-05-23 Mustafa Sabri Kilic , Martin Z. Bazant , Armand Ajdari

The charge distribution at the interface between two electrolytes is studied for the case of non-vanishing ion fluxes. The analysis is an extension of the established Verwey-Niessen theory to non-equilibrium situations. Applying matched…

Soft Condensed Matter · Physics 2011-05-03 Steffen Hardt , Tobias Baier

Charge inversion occurring for smeared-out ions is accompanied by an oscillatory charge density profile, indicating a layering of an alternating charge. The layering effect, however, is not coextensive with charge inversion, and charge…

Soft Condensed Matter · Physics 2016-11-14 Derek Frydel

Non-local electrostatic interactions associated with the finite solvent size and ion polarizability are investigated within the mean-field linear response theory. To this end, we introduce a field theoretic model of a polar liquid composed…

Soft Condensed Matter · Physics 2015-06-15 Sahin Buyukdagli , Tapio Ala-Nissila

We investigate the phenomenon of counterion condensation in a solution of highly charged rigid polyelectrolytes within the cell model. A method is proposed which -- based on the charge distribution function -- identifies both the fraction…

Soft Condensed Matter · Physics 2009-10-31 Markus Deserno , Christian Holm , Sylvio May

Ions in ionic liquids and concentrated electrolytes reside in a crowded, strongly-interacting environment, leading to the formation of discrete layers of charges at interfaces. Here, we propose a continuum theory that captures the…

We investigate a double-layer of penetrable ions near a charged wall. We find a new mechanism for charge reversal that occurs in the weak-coupling regime and, accordingly, the system is suitable for the mean-field analysis. The…

Soft Condensed Matter · Physics 2013-05-06 Derek Frydel , Yan Levin

We apply general variational techniques to the problem of the counterion distribution around highly charged objects where strong condensation of counterions takes place. Within a field-theoretic formulation using a fluctuating electrostatic…

Soft Condensed Matter · Physics 2009-11-07 Roland R. Netz , Henri Orland

The modified Poisson-Boltzmann theory of the restricted primitive model double layer is revisited and recast in a fresh, slightly broader perspective. Derivation of relevant equations follow the techniques utilized in the earlier MPB4 and…

Statistical Mechanics · Physics 2017-10-05 L. B. Bhuiyan , C. W. Outhwaite

Whereas the majority of ions in the bulk of a solvent-free ionic liquid is bound into clusters, this is expected to change in the electrical double layer (EDL), in which the resulting electric field 'prefers' to interact with electrical…

Chemical Physics · Physics 2020-04-27 Yufan Zhang , Ting Ye , Ming Chen , Zachary Goodwin , Jun Huang , Guang Feng , Alexei Kornyshev

Correlation functions in concentrated ionic systems are studied within the mesoscopic theory at the level of the Gaussian approximation. The previously neglected fluctuation contribution to the inverse charge-charge correlation function is…

Soft Condensed Matter · Physics 2025-06-26 O. Patsahan , A. Ciach

The Poisson-Boltzmann (PB) theory is widely used to depict ionic systems. As a mean-field theory, the PB theory neglects the correlation effect in the ionic atmosphere and leads to deviations from experimental results as the concentration…

Soft Condensed Matter · Physics 2019-06-25 Mao Su , Zhijie Xu , Yanting Wang