The role of multipoles in counterion-mediated interactions between charged surfaces: strong and weak coupling

Kanduč, Matej; Naji, Ali; Jho, YongSeok; Pincus, P.; Podgornik, Rudolf

doi:10.1088/0953-8984/21/42/424103

Cited by 47 publications

(86 citation statements)

References 42 publications

(113 reference statements)

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“…One example of this is the PB treatment of primitive model electrolyte systems. When the true properties of the primitive model were evaluated with accurate statistical mechanical methods, many new features were found beyond PB approximation ͑Ben- Yaakov et al, 2009;Kanduc, Naji, Jho, Pincus, and Podgornik, 2009͒. Several of the observed deviations between experiments and the PB prediction were due to the mathematical approximations implicit in the PB approach and not due to the underlying model.…”

Section: Challenges and Opportunitiesmentioning

confidence: 99%

Long range interactions in nanoscale science

et al. 2010

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Our understanding of the "long range" electrodynamic, electrostatic, and polar interactions that dominate the organization of small objects at separations beyond an interatomic bond length is reviewed. From this basic-forces perspective, a large number of systems are described from which one can learn about these organizing forces and how to modulate them. The many practical systems that harness these nanoscale forces are then surveyed. The survey reveals not only the promise of new devices and materials, but also the possibility of designing them more effectively.

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Section: Challenges and Opportunitiesmentioning

confidence: 99%

Long range interactions in nanoscale science

et al. 2010

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“…Different generalized PB approaches based on dielectric continuum but accounting for the multipolar moments of ions were also developed in Refs. [19,20]. We have recently extended the DPB formalism of Ref.…”

Section: Introductionmentioning

confidence: 99%

Microscopic formulation of nonlocal electrostatics in polar liquids embedding polarizable ions

2013

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Nonlocal electrostatic interactions associated with 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 of linear multipole solvent molecules and embedding polarizable ions modeled as Drude oscillators. Unlike previous dipolar Poisson-Boltzmann formulations treating the solvent molecules as point dipoles, our model is able to qualitatively reproduce the non-local dielectric response behavior of polar liquids observed in molecular dynamics simulations and atomic force microscope experiments for water solvent at charged interfaces. The present theory explains the formation of the associated interfacial hydration layers in terms of a cooperative dipolar response mechanism driven by the reaction of the solvent molecules to their own polarization field. We also incorporate into the theory the relative multipole moments of water molecules obtained from quantum mechanical calculations and show that the multipolar contributions to the dielectric permittivity are largely dominated by the dipolar one. We find that this stems from the mutual cancellation of the first two interfacial hydration layers of opposite net charge for multipolar liquids. Within the same nonlocal dielectric response theory, we show that the induced ion polarizability reverses the interfacial ion density trends predicted by the Poisson-Boltzmann theory, resulting in a surface affinity of coions and exclusion of counterions. The results indicate that the consideration of the discrete charge composition of solvent molecules and ions is the key step towards a microscopic understanding of nonlocal electrostatic effects in polar solvents.

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“…Kanduč et al 39 studied symmetrically charged planar surfaces with a dielectric mismatch on both sides and counterions with multipole moments in between. In the weak coupling regime, they derived a PB theory for counterion density in the case where the counterions possess dipolar and quadrupolar moments.…”

Section: Introductionmentioning

confidence: 99%

“…44 The influence of dielectric inhomogeneities has also been analyzed. 39,45,46 Recently, Turesson et al 47 considered charged stiff polyelectrolytes and their role in intersurface interactions. It was shown that in the limit of infinitely stiff chains, the bridging attraction is lost and is replaced by a strong correlation attraction at short distances.…”

Section: Introductionmentioning

confidence: 99%

The properties of dimers confined between two charged plates

Hatlo

Bohinc

Lue

2010

The Journal of Chemical Physics

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We consider two like-charged planar surfaces immersed in solution of oppositely charged dimer counterions with a bond length l. To analyze this system, we extend and employ a self-consistent field theory that has been shown to be accurate from the weak to the intermediate through to the strong coupling regimes. In the limit of very short dimers, the results converge to the results for pointlike divalent ions. Near the surfaces, the dimers lie parallel to the charged plates. In the intermediate coupling regime, the dimers are aligned perpendicularly to the surface when they are a distance l from a surface. In the weak coupling regime, the interactions are only repulsive. At slightly higher couplings, there is a minimum in the variation of the free energy with distance at approximately the bond length of the dimers, which arises from bridging conformations of the dimers. In the intermediate coupling regime, an additional minimum in the free energy is observed at much smaller distances, which is due to the correlations between the dimers. For large dimer bond lengths, this minimum is metastable with respect to the previous minimum. However, as the bond length decreases, this minimum becomes the stable, while the minimum associated with the dimer bond length becomes metastable and eventually disappears. For shorter dimer bond length the attractive interaction is the result of correlations between counterions and charges on the surfaces. We find that dimers can mediate attractive interaction between like-charged surfaces in the intermediate coupling regime. The analysis of orientations confirms the bridging mechanism for sufficiently long dimers, whereas at high electrostatic couplings charge correlations contribute to the attraction.

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The role of multipoles in counterion-mediated interactions between charged surfaces: strong and weak coupling

Cited by 47 publications

References 42 publications

Long range interactions in nanoscale science

Long range interactions in nanoscale science

Microscopic formulation of nonlocal electrostatics in polar liquids embedding polarizable ions

The properties of dimers confined between two charged plates

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