A review of steric interactions of ions: Why some theories succeed and others fail to account for ion size

Gillespie, Dirk

doi:10.1007/s10404-014-1489-5

Cited by 94 publications

(97 citation statements)

References 82 publications

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“…Specifically, the SLIC/MSA model adds a simple nonlinear perturbation of the usual dielectric boundary condition, involving the square root of the local electric field at the boundary (Equation 18). The fact that the SLIC/MSA model can reproduce the MSA results using only the normal electric field, without relying on the solute radius, suggest it may offer at least qualitative improvements for more complicated molecules such as proteins or DNA.…”

Section: Discussionmentioning

confidence: 99%

“…The h(E n ) at T = 25 and 75°C are shown in Figure 1; the solid lines are from Equation (17) and the points are from Equation (18). It can be observed that as E n approaches zero (i.e.…”

Section: Deriving a Multiscale Boundary Condition From The Msamentioning

confidence: 95%

“…However, standard PB models neglect important physical phenomena such as correlations between solvent molecules (including both water and ions) [12,13]. Numerous modified PB models for strong electrolytes address ion packing effects and correlations [14][15][16][17][18] but fewer address the equivalent challenges for water itself. Popular approaches for water's non-bulk response include modelling saturation via nonlinear dielectric theory [19][20][21][22] and solvent dipole correlations via nonlocal dielectric theory [23][24][25][26].…”

Section: Introductionmentioning

confidence: 99%

“…The main use of the MSA here is to determine the single fitting parameter in our model. This kind of localisation has been used in conjunction with the MSA to define electrostatic correlation structure in classical density functional theory [18,34], as well as dielectric correlations [35].…”

Section: Introductionmentioning

confidence: 99%

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Generalising the mean spherical approximation as a multiscale, nonlinear boundary condition at the solute–solvent interface

2016

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In this paper, we extend the familiar continuum electrostatic model to incorporate finite-size effects in the solvation layer, by perturbing the usual macroscopic interface condition. The perturbation is based on the mean spherical approximation (MSA), to derive a multiscale solvation-layer interface condition (SLIC/MSA). We show that SLIC/MSA reproduces MSA predictions for Born ions in a variety of polar solvents, including water as well as other protic and aprotic solvents. Importantly, the SLIC/MSA model predicts not only solvation free energies accurately but also solvation entropies, which standard continuum electrostatic models fail to predict. The SLIC/MSA model depends only on the normal electric field at the dielectric boundary, similar to our recent development of a SLIC model for charge-sign hydration asymmetry, and the reformulation of the MSA as an effective boundary condition enables its straightforward application to complex molecules such as proteins, whereas traditionally it is primarily a bulk theory. This work also opens the possibility for other electrolyte models to be incorporated into fast implicit-solvent models of biomolecular electrostatics.

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Section: Discussionmentioning

confidence: 99%

“…The h(E n ) at T = 25 and 75°C are shown in Figure 1; the solid lines are from Equation (17) and the points are from Equation (18). It can be observed that as E n approaches zero (i.e.…”

Section: Deriving a Multiscale Boundary Condition From The Msamentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Generalising the mean spherical approximation as a multiscale, nonlinear boundary condition at the solute–solvent interface

2016

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“…This is comprised of an ideal (entropic) component and a residual component, which accounts for all non-electrostatic non-ideality. The use of the LDA can lead to artifacts in the prediction of the properties of the EDL [33]. While these are not significant at low concentrations and applied potentials, they can lead to qualitative inaccuracies at more severe conditions.…”

Section: Reference Systemmentioning

confidence: 99%

The influence of excluded volume and excess ion polarisability on the capacitance of the electric double layer

Minton

Lue

2016

Molecular Physics

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This version is available at https://strathprints.strath.ac.uk/55894/ Strathprints is designed to allow users to access the research output of the University of Strathclyde. Unless otherwise explicitly stated on the manuscript, Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Please check the manuscript for details of any other licences that may have been applied. You may not engage in further distribution of the material for any profitmaking activities or any commercial gain. You may freely distribute both the url (https://strathprints.strath.ac.uk/) and the content of this paper for research or private study, educational, or not-for-profit purposes without prior permission or charge.Any correspondence concerning this service should be sent to the Strathprints administrator: strathprints@strath.ac.ukThe Strathprints institutional repository (https://strathprints.strath.ac.uk) is a digital archive of University of Strathclyde research outputs. It has been developed to disseminate open access research outputs, expose data about those outputs, and enable the management and persistent access to Strathclyde's intellectual output. We apply a modified Poisson-Boltzmann theory which permits ions of different sizes and excess polarizabilities to the study of these properties' effects on the differential capacitance of the electric double layer. For a planar electrode, we find an analytical expression for the differential capacitance, which is examined in the limits of low and high applied potential. In the low potential limit, a reduction of the solution relative permittivity caused by the ion polarizability causes the differential capacitance to decrease above a certain concentration, relative to the Gouy-Chapman-Stern theory. A similar effect is observed for the excluded volume, but only if the ions are of different sizes. In the high potential limit, the differential capacitance decreases inversely with the square root of the applied voltage. In a mixed electrolyte, asymmetries in both ion size and excess polarizability alter the surface adsorption of species: at high potentials, smaller ions displace larger ions and less polarizable ions displace more polarizable ions. The extent of the displacement agrees favorably with experimental data. A further consequence of this displacement is the appearance of a second peak in the differential capacitance, which is enhanced by excess ion polarizability.

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Solvent‐mediated nonelectrostatic ion–ion interactions predicting anomalies in electrophoresis

et al. 2017

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We study the effects of solvent-mediated nonelectrostatic ion-ion interactions on electrophoretic mobility of a charged spherical particle. To this end, we consider the case of low surface electrostatic potential resulting in the linearization of the governing equations, which enables us to deduce a closed-form analytical solution to the electrophoretic mobility. We subsequently compare our results to the standard model using Henry's approach and report the changes brought about by the nonelectrostatic potential. The classical approach to determine the electrophoretic mobility underpredicts the particle velocity when compared with experiments. We show that this issue can be resolved by taking into account nonelectrostatic interactions. Our analysis further reveals the phenomenon of electrophoretic mobility reversal that has been experimentally observed in numerous previous studies.

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A review of steric interactions of ions: Why some theories succeed and others fail to account for ion size

Cited by 94 publications

References 82 publications

Generalising the mean spherical approximation as a multiscale, nonlinear boundary condition at the solute–solvent interface

Generalising the mean spherical approximation as a multiscale, nonlinear boundary condition at the solute–solvent interface

The influence of excluded volume and excess ion polarisability on the capacitance of the electric double layer

Solvent‐mediated nonelectrostatic ion–ion interactions predicting anomalies in electrophoresis

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