Exclusion Volume Term in the Inhomogeneous Poisson−Boltzmann Theory for High Surface Charge

Lamperski, Stanisław; Outhwaite, C.W.

doi:10.1021/la011852v

Cited by 64 publications

(62 citation statements)

References 18 publications

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“…which is consistent with the classical PB theory for dimensionless (point-like) ions and constant permittivity (McLaughlin 1989;Cevc 1990;Kralj-Iglič and Iglič 1996;Lamperski and Outhwaite 2002;Bivas 2006 The charges of counterions, coions and water molecules (Langevin dip average microscopic volume charge density: The polarization P is given by:…”

Section: Theoretical Predictionssupporting

confidence: 81%

“…the electrical double layer (EDL) (Helmholtz 1879;Gouy 1910;Chapman 1913;Stern 1924). The distribution of ions in the EDL can be described within the Poisson-Boltzmann (PB) theory (McLaughlin 1989;KraljIglič and Iglič 1996;Lamperski and Outhwaite 2002;Bivas 2006;Bivas and Ermakov 2007), expressing the competition between electrostatic interactions and the entropy of ions in the solution. Due to the electrostatic forces between the charged surface and ions in the solution, counter-ions are accumulated close to the charged surface, while coions are depleted from this region.…”

Section: Introductionmentioning

confidence: 99%

“…This phenomenon is also subject of the present work. Most of the PB models of EDL (McLaughlin 1989;Cevc 1990;Lamperski and Outhwaite 2002) assume that the dielectric permittivity in the electrolyte is constant. In the absence of an explicit consideration of orientational ordering of water molecules, the assumption of constant permittivity is the consequence of the constant number of water molecules in PB theory.…”

Section: Introductionmentioning

confidence: 99%

“…The finite volume of ions (Bikerman 1942;Kralj-Iglič and Iglič 1996;Lamperski and Outhwaite 2002;Iglič et al 2010) in the electrolyte solution (i.e. the excluded volume effect) is not taken into account.…”

Section: Introductionmentioning

confidence: 99%

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Langevin Poisson-Boltzmann equation: point-like ions and water dipoles near a charged surface

Gongadze

Rienen²,

Kralj-Iglič³

et al. 2011

gpb

104

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Abstract. Water ordering near a charged membrane surface is important for many biological processes such as binding of ligands to a membrane or transport of ions across it. In this work, the mean-field Poisson-Boltzmann theory for point-like ions, describing an electrolyte solution in contact with a planar charged surface, is modified by including the orientational ordering of water. Water molecules are considered as Langevin dipoles, while the number density of water is assumed to be constant everywhere in the electrolyte solution. It is shown that the dielectric permittivity of an electrolyte close to a charged surface is decreased due to the increased orientational ordering of water dipoles. The dielectric permittivity close to the charged surface is additionally decreased due to the finite size of ions and dipoles.

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Section: Theoretical Predictionssupporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Langevin Poisson-Boltzmann equation: point-like ions and water dipoles near a charged surface

Gongadze

Rienen²,

Kralj-Iglič³

et al. 2011

gpb

104

View full text Add to dashboard Cite

show abstract

“…Another modified PB model, ignoring the fluctuation correction but with a more advanced treatment of exclusion volume factors for planar systems, involving bulk hard-sphere correlation functions, was proposed. 74 It allowed to reproduce Monte-Carlo results for a nonmonotonic decay of counterion concentration near a highly charged surface. The model was also extended by accounting for the finite size of solvent molecules, 75 but it was not yet applied for realistic asymmetric problems like macromolecules of arbitraryshape.…”

Section: Modified Npbe With Ionic Correlations and Fluctuationsmentioning

confidence: 99%

Continuum molecular electrostatics, salt effects, and counterion binding—A review of the Poisson–Boltzmann theory and its modifications

2007

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This work is a review of the Poisson–Boltzmann (PB) continuum electrostatics theory and its modifications, with a focus on salt effects and counterion binding. The PB model is one of the mesoscopic theories that describes the electrostatic potential and equilibrium distribution of mobile ions around molecules in solution. It serves as a tool to characterize electrostatic properties of molecules, counterion association, electrostatic contributions to solvation, and molecular binding free energies. We focus on general formulations which can be applied to large molecules of arbitrary shape in all‐atomic representation, including highly charged biomolecules such as nucleic acids. These molecules present a challenge for theoretical description, because the conventional PB model may become insufficient in those cases. We discuss the conventional PB equation, the corresponding functionals of the electrostatic free energy, including a connection to DFT, simple empirical extensions to this model accounting for finite size of ions, the modified PB theory including ionic correlations and fluctuations, the cell model, and supplementary methods allowing to incorporate site‐bound ions in the PB calculations. © 2007 Wiley Periodicals, Inc. Biopolymers 89: 93–113, 2008.This article was originally published online as an accepted preprint. The “Published Online” date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com

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Understanding the Electric Double Layer at the Electrode‐Electrolyte Interface: Part I – No Ion Specific Adsorption

Mazur,

Brandyshev,

Doronin

et al. 2024

ChemPhysChem

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We present a comprehensive mean‐field model that takes into account the key components of modern electrical double layer theory at the interface between an electrode and an electrolyte solution. The model considers short‐range specific interactions between different species, including electrode‐ion repulsion, the hydration of ions, dielectric saturation of solvent (water), and excluded volume (steric) interactions between species. By solving a modified Poisson‐Boltzmann equation and using the appropriate results of quantum chemistry calculations on the hydration of ions, we can accurately approximate the differential capacitance profiles of aqueous electrolyte solutions at the boundary with a silver electrode. The specific interactions between the ions and the electrodes in the systems under consideration are assumed to be significantly weaker than their Coulomb interactions. A novel aspect of our research is the investigation of the impact of short‐range ion‐water interactions on the differential capacitance, which provides new insights into the behavior of the electrical double layer. This model holds the potential to be useful for electrochemical engineers working on the development of supercapacitors and related electrochemical energy storage devices. It serves as a basis for future modeling of electrolyte systems on real electrodes, especially in scenarios where chemical ion‐electrode interactions are significant.

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Exclusion Volume Term in the Inhomogeneous Poisson−Boltzmann Theory for High Surface Charge

Abstract: A restricted primitive model electrolyte in the neighborhood of a uniformly charged plane electrode is investigated at high surface charge using an improved Poisson−Boltzmann theory. A layering of counterions is found in agreement with Monte Carlo simulations.

Cited by 64 publications

References 18 publications

Langevin Poisson-Boltzmann equation: point-like ions and water dipoles near a charged surface

Langevin Poisson-Boltzmann equation: point-like ions and water dipoles near a charged surface

Continuum molecular electrostatics, salt effects, and counterion binding—A review of the Poisson–Boltzmann theory and its modifications

Understanding the Electric Double Layer at the Electrode‐Electrolyte Interface: Part I – No Ion Specific Adsorption

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