Field theory of structured liquid dielectrics

Blossey, Ralf; Podgornik, Rudolf

doi:10.1103/physrevresearch.4.023033

Cited by 8 publications

(23 citation statements)

References 42 publications

(70 reference statements)

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“…We assume that for a univalent electrolyte the chemical potentials satisfy µ ± = µ − = µ + , while a 3 is the volume of a site in the lattice gas partition function. Apart from the contribution of the polarizability on the Drude model level, the expression matches the one derived before [7]. We also note that in the pure electrostatic case (E = 0, see below) and with equal polarizability for the solvent and solute species, the polarizability terms decouple from the rest of the free energy.…”

Section: Bulk Equationssupporting

confidence: 76%

“…In our previous work we considered a structured liquid dielectric described by charge density and solvent polarization in a harmonic approximation and formulated the corresponding field theory for a bulk system [7]. Here, we first revisit the formulation of this theory by including the polarizability of the solvent dipoles, the non-electrostatic dipole-dipole interaction and the charge-dipole hydration coupling.…”

Section: A Continuum Model For a Polarizable Dipole-ion Mixturementioning

confidence: 99%

“…In our previous work we have discussed different versions of the bulk model in order to clarify the role the different bulk lengths play in the polarization interactions [7].…”

Section: Solving the Model Equationsmentioning

confidence: 99%

“…In this paper we take up this challenge by developing a comprehensive fieldtheoretic continuum model extending standard Poisson-Boltzmann-type theories. The starting point of our analysis is our recently developed field theory of structured dielectrics [7], in which the bulk theory was developed based on a two-order parameter description in terms of charge density and polarization. In the development of this theory we were guided by the Onsager-Dupuis theory of the dielectric properties of ice [8][9][10][11].…”

Section: Introductionmentioning

confidence: 99%

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A comprehensive continuum theory of structured liquids

Blossey¹,

Podgornik²

2022

Preprint

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We develop a comprehensive continuum model capable of treating both electrostatic and structural interactions in liquid dielectrics. Starting from a twoorder parameter description in terms of charge density and polarization, we derive a field-theoretic model generalizing previous theories. Our theory explicitly includes electrostatic and structural interactions in the bulk of the liquid and allows for polarization charges within a Drude model. In particular, we develop a detailed description of the boundary conditions which include the charge regulation mechanism and surface polarization. The general features for solving the saddle-point equations of our model are elucidated and future applications to predict and validate experimental results are outlined.

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Section: Bulk Equationssupporting

confidence: 76%

Section: A Continuum Model For a Polarizable Dipole-ion Mixturementioning

confidence: 99%

“…In our previous work we have discussed different versions of the bulk model in order to clarify the role the different bulk lengths play in the polarization interactions [7].…”

Section: Solving the Model Equationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A comprehensive continuum theory of structured liquids

Blossey¹,

Podgornik²

2022

Preprint

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“…This has been first consistently formulated in Ref. [42] by assuming a mixture of dipolar solvent molecules and monopolar electrolyte ions, interacting via electrostatic and non-electrostatic structural interatctions.…”

mentioning

confidence: 99%

Continuum theories of structured dielectrics

Blossey

Podgornik

2022

EPL

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Aqueous dielectrics are ubiquitous in soft- and bio-nano matter systems. The theoretical description of such systems in terms of continuum (“macroscopic”) theory remains a serious challenge. In this perspective we first review the existing continuum phenomenological approaches that have been developed in the past decades. In order to describe a path to advance continuum theory beyond these approaches we then take recourse to the Onsager-Dupuis theory of the dielectric behaviour of ice, which, for the case of a solid dielectric, exemplified important conceptual issues we deem relevant for the development of a more fundamental continuum theory of liquid dielectrics. Subsequently, we discuss our recently proposed continuum field theory of structured dielectrics, which provides a generalized approach to the dielectric behavior of such systems.

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The Dramatic Effect of Water Structure on Hydration Forces and the Electrical Double Layer

2023

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Forces between hydrophilic surfaces mediated by water are important in various systems from lipid membranes and solid surfaces to colloids and macromolecules, first discovered as a significant addition to DLVO forces at the nanoscale. These “hydration forces” have been studied in great detail experimentally using osmotic stress measurements, surface force apparatus, and AFM, and they have also been the subject of multiple theories and simulations. One spectacular feature observed in experimental and simulation studies was the nonmonotonic, oscillatory decay in the forces between atomically smooth surfaces. Forces between “rougher” surfaces exhibit only quasi-exponential, monotonic decay. Here we revisit this hydration force problem by exploring the consequences of an extended phenomenological Landau–Ginzburg approach that describes nonlocal correlations in water, linking them with the key features of the wave-number k-dependent nonlocal dielectric function of water. With corresponding boundary conditions, this theory predicts the observed oscillatory decay in hydration force between ideally flat surfaces, the oscillatory mode disappearing with just a tiny roughness of the surfaces (of mean height ca. of the size of a water molecule). This study also brings an important side message. Explanation of these observations appears only possible under an assumption of two modes of polarization in water, consistent with the behavior of the response function, i.e., Lorentzian at small k and resonance-like at higher k. This resolves the “force oscillation–non-oscillation” paradigm, which is a strong, although indirect indication of the existence of these two modes. We also consider other important subjects, such as how the distribution of ions near a charged surface reacts to the propensity for overscreening oscillations due to polarized water. This is important not only for the interactions between charged surfaces but also for the fundamental understanding of the structure of the electrical double layer at electrochemical interfaces. We show that even in dilute electrolytes, the distribution of ions in the vicinity of the polarized interface follows, although not literally, preferential positions corresponding to the potential wells caused by “resonance” water layering. For a sharp interface, the theory predicts that the decaying spatial oscillation profiles extend over a 1 to 2 nm distance from the interface. With the smearing of the interface and the corresponding suppression of the resonance water layering, oscillations in the spatial distribution of ions subside, resulting in a familiar Gouy–Chapman–Stern picture. At longer distances from the interface, whether smeared or not, the ion distribution profiles become Gouy–Chapman-like. The effect of the boundary conditions on water polarization at the interface goes beyond a trivial shift of the potential of zero charge. We show that they can dramatically affect the ion distribution near the charged surface. Last, but not least, we study how the interfacial water layerin...

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Field theory of structured liquid dielectrics

Cited by 8 publications

References 42 publications

A comprehensive continuum theory of structured liquids

A comprehensive continuum theory of structured liquids

Continuum theories of structured dielectrics

The Dramatic Effect of Water Structure on Hydration Forces and the Electrical Double Layer

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