Electrostatic interactions in strongly coupled soft matter

Naji, Ali; Jungblut, Swetlana; Moreira, André G.; Netz, Roland R.

doi:10.1016/j.physa.2004.12.029

Cited by 183 publications

(392 citation statements)

References 118 publications

(466 reference statements)

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“…The unmodified PB equation for a uniformly charged cylinder may be inadequate in describing the interaction for a variety of reasons. Correlation effects [1][2][3][4][5][6][7][8][9][10][11], image charge effects [1,5,8,10,12,13], solvent effects [12,[14][15][16][17][18][19], and structure of charged groups at the macro-ion surface [1,12,[19][20][21][22] may all play an important role. Though, the relative degree of each of these effects is likely to depend on the particular properties of the type of macro-ion under consideration, most importantly its shape, charge density and surface charge distribution of fixed charged groups.…”

Section: Introductionmentioning

confidence: 99%

“…Correlation effects may lead to two predicted phenomena, that of charge inversion [1,7,23,24] and samecharge attraction [1,3,5,7,9,11,25]. In charge inversion, the amount of positive charge, due to counter-ions, exceeds the surface charge density of the macro-ion effectively making it of opposite charge to its fixed charged groups.…”

Section: Introductionmentioning

confidence: 99%

“…It arises from the charges on one molecule experiencing the force due image charges of themselves on the other molecule. Beyond the Poisson-Boltzmann equation, image charge effects in the interaction of individual ions with the small macro-ion may also become important [5,10]. Here, the effects could be quite subtle.…”

mentioning

confidence: 99%

“…Here, the effects could be quite subtle. Image charge effects may increase the threshold at which correlation effects cause attraction, in terms of surface charge density and ionic valance [5]; but, in certain cases, they may cause increased attraction [10]. Other important effects could arise from the discreteness of the solvent.…”

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confidence: 99%

“…Such self-consistent approximations have enjoyed notable success in other areas of condensed matter physics, and may yet provide a new useful line of attack in understanding polyelectrolyte interactions. These particular field theories, which arise from such models, enjoy another important advantage: one can do a strong-coupling expansion [3,5,10]. Such an expansion is valid when the ions in solution are highly correlated.…”

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confidence: 99%

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Correlation effects, image charge effects and finite size in the macro-ion-electrolyte system: A field-theoretic approach

Lee

2009

Eur. Phys. J. E

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Abstract. We consider a model of a macro-ion surrounded by small ions of an electrolyte solution. The finite size of ionic charge distributions of ions, and image charge effects are considered. From such a model it is possible to construct a statistical field theory with a single fluctuating field and derive physical interpretations for both the mean field and two-point correlation function. For point-like charges, at the level of a Gaussian (or saddle point) approximation, we recover the standard Poisson-Boltzmann equation. However, to include ionic correlation effects, as well as image charge effects of individual ions, we must go beyond this. From the field theory considered, it is possible to construct self-consistent approximations. We consider the simplest of these, namely the Hartree approximation. The Hartree equations take the form of two coupled equations. One is a modified Poisson-Boltzmann equation; the other describes both image charge effects on the individual ions, as well as correlations. Such equations are difficult to solve numerically, so we develop an (a WKB-like) approximation for obtaining approximate solutions. This, we apply to a uniformly charged rod in univalent electrolyte solution, for point like ions, as well as for extended spherically symmetric distributions of ionic charge on electrolyte ions. The solutions show how correlation effects and image charge effects modify the Poisson-Boltzmann result. Finite-size charge distributions of the ions reduce both the effects of correlations and image charge effects. For point charges, we test the WKB approximation by calculating a leading-order correction from the exact Hartree result, showing that the WKB-like approximation works reasonably well in describing the full solution to the Hartree equations. From these solutions, we also calculate an effective charge compensation parameter in an analytical formula for the interaction of two charged cylinders.PACS. 61.20.Qg Structure of associated liquids: electrolytes, molten salts, etc. -61.20.Gy Theory and models of liquid structure -82.35.Rs Polyelectrolytes

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Correlation effects, image charge effects and finite size in the macro-ion-electrolyte system: A field-theoretic approach

Lee

2009

Eur. Phys. J. E

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Applications of Synchrotron‐Based Spectroscopic Techniques in Studying Nucleic Acids and Nucleic‐Acid‐Based Nanomaterials

McGhee

et al. 2018

Synchrotron Radiation in Materials Science

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Strong‐Coupling Theory for a Polarizable Planar Colloid

Šamaj

Trizac

2012

Contrib. Plasma Phys.

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We propose a strong-coupling analysis of a polarizable planar interface, in the spirit of a recently introduced Wigner-Crystal formulation. The system is made up of two moieties: a semi-infinite medium (z < 0) with permittivity ε ′ while the other half space in z > 0 is occupied by a solution with permittivity ε, and mobile counter-ions (no added electrolyte). The interface at z = 0 bears a uniform surface charge. The counter-ion density profile is worked out explicitly for both repulsive and attractive dielectric image cases.Copyright line will be provided by the publisher Introduction. Strong coulombic couplings can conveniently be realized in colloidal systems by increasing the valence of micro-ions [1, 2, 3]. The counter-intuitive effects such as like-charge attraction or overcharging that ensue [1,2,3], have been mostly studied under the simplifying assumption that the dielectric permittivity of colloidal particles coincides with that of the surrounding solvent -assumed to be a structure-less medium, characterized by its sole static dielectric response. However, realistic systems, of biological interest in particular, often exhibit highly inhomogeneous dielectric structure, with polarizable colloids having a static dielectric constant (ε ′ ≤ 10), much smaller than that of the solvent (ε ≃ 80 for water). It is therefore desirable to include colloidal polarizability into existing strong-coupling treatments (see below for a precise definition of the relevant coupling parameter). This is the purpose of the present contribution.To our knowledge, the dielectric inhomogeneities were studied in the leading strong-coupling order only for the geometry of two parallel plates [4] where counter-ions are confined in a slab, and similarly in Ref. [5], for a spherical macro-ion in a concentric spherical Wigner-Seitz cell. It was realized that while the image charge effects are generally small in the weak-coupling regime, they become relevant in the strong-coupling limit. Our goal here is to obtain exact results for a single polarizable planar colloid (hatched region in Fig. 1), in the strong-coupling limit (see Fig. 1 for a definition of the coupling parameter Ξ). To this end, the Wigner-Crystal formulation of Strong-Coupling (SC) theory, recently introduced [6], is modified to account for dielectric image charges. We emphasize that this approach has been shown to be in excellent agreement with Monte Carlo simulations, in contrast to previous fugacity SC expansions [3]. The idea is to consider the first relevant large Ξ excitations around the ground state structure, that is a Wigner Crystal realized when, strictly speaking, Ξ → ∞ [6].

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Electrostatic interactions in strongly coupled soft matter

Cited by 183 publications

References 118 publications

Correlation effects, image charge effects and finite size in the macro-ion-electrolyte system: A field-theoretic approach

Correlation effects, image charge effects and finite size in the macro-ion-electrolyte system: A field-theoretic approach

Applications of Synchrotron‐Based Spectroscopic Techniques in Studying Nucleic Acids and Nucleic‐Acid‐Based Nanomaterials

Strong‐Coupling Theory for a Polarizable Planar Colloid

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