Structure of electrolyte solutions at nonuniformly charged surfaces on a variety of length scales.

The structures of dilute electrolyte solutions close to nonuniformly charged planar substrates are systematically studied within the entire spectrum of microscopic to macroscopic length scales by means of a unified classical density functional theory approach. This is in contrast to previous investigations, which are applicable either to short or to long length scales. It turns out that interactions with microscopic ranges, e.

The role of counterions in ionic liquid crystals.

Previous theoretical studies of calamitic (i.e., rod-like) ionic liquid crystals (ILCs) based on an effective one-species model led to indications of a novel smectic-A phase with a layer spacing being much larger than the length of the mesogenic (i.

Heterogeneous surface charge confining an electrolyte solution.

The structure of dilute electrolyte solutions close to a surface carrying a spatially inhomogeneous surface charge distribution is investigated by means of classical density functional theory within the approach of fundamental measure theory. For electrolyte solutions, the influence of these inhomogeneities is particularly strong because the corresponding characteristic length scale is the Debye length, which is large compared to molecular sizes. Here, a fully three-dimensional investigation is performed, which accounts explicitly for the solvent particles, and thus provides insight into effects caused by ion-solvent coupling.

Charge regulation radically modifies electrostatics in membrane stacks.

Motivated by biological membrane-containing organelles in plants and photosynthetic bacteria, we study charge regulation in a model membrane stack. Considering (de)protonation as the simplest mechanism of charge equilibration between the membranes and with the bathing environment, we uncover a symmetry-broken charge state in the stack with a quasiperiodic effective charge sequence. In the case of a monovalent bathing salt solution our model predicts complex, inhomogeneous charge equilibria depending on the strength of the (de)protonation reaction, salt concentration, and membrane size.

Transient response of an electrolyte to a thermal quench.

We study the transient response of an electrolytic cell subject to a small, suddenly applied temperature increase at one of its two bounding electrode surfaces. An inhomogeneous temperature profile then develops, causing, via the Soret effect, ionic rearrangements towards a state of polarized ionic charge density q and local salt density c. For the case of equal cationic and anionic diffusivities, we derive analytical approximations to q,c, and the thermovoltage V_{T} for early (t≪τ_{T}) and late (t≫τ_{T}) times as compared to the relaxation time τ_{T} of the temperature.

Interface structures in ionic liquid crystals.

Ionic liquid crystals (ILCs) are anisotropic mesogenic molecules which additionally carry charges. This combination gives rise to a complex interplay of the underlying (anisotropic) contributions to the pair interactions. It promises interesting and distinctive structural and orientational properties to arise in systems of ILCs, combining properties of liquid crystals and ionic liquids.

A ferronematic slab in external magnetic fields.

The behavior of a uniformly magnetized ferronematic slab is investigated numerically in a situation in which an external magnetic field is applied parallel and antiparallel, respectively, to its initial magnetization direction. The employed numerical method allows one to determine hysteresis curves from which a critical magnetic field strength (i.e.

Interfacial premelting of ice in nano composite materials.

The interfacial premelting in ice/clay nano composites was studied by high energy X-ray diffraction. Below the melting point of bulk water, the formation of liquid water was observed for the ice/vermiculite and ice/kaolin systems. The liquid fraction is gradually increasing with temperature.

Electrostatic interaction of particles trapped at fluid interfaces: effects of geometry and wetting properties.

The electrostatic interaction between pairs of spherical or macroscopically long, parallel cylindrical colloids trapped at fluid interfaces is studied theoretically for the case of small inter-particle separations. Starting from the effective interaction between two planar walls and by using the Derjaguin approximation, we address the issue of how the electrostatic interaction between such particles is influenced by their curvatures and by the wetting contact angle at their surfaces. Regarding the influence of curvature, our findings suggest that the discrepancies between linear and nonlinear Poisson-Boltzmann theory, which have been noticed before for planar walls, also occur for spheres and macroscopically long, parallel cylinders, though their magnitude depends on the wetting contact angle.

Microphase separation and the formation of ion conductivity channels in poly(ionic liquid)s: A coarse-grained molecular dynamics study.

We study generic properties of poly(ionic liquid)s (PILs) via coarse-grained molecular dynamics simulations in bulk solution and under confinement. The influence of different side chain lengths on the spatial properties of the PIL systems and on the ionic transport mechanism is investigated in detail. Our results reveal the formation of apolar and polar nanodomains with increasing side chain length in good agreement with previous results for molecular ionic liquids.

Correction: Surface induced smectic order in ionic liquids - an X-ray reflectivity study of [CCim][NTf].

Correction for 'Surface induced smectic order in ionic liquids - an X-ray reflectivity study of [CCim][NTf]' by Julian Mars et al., Phys. Chem.

Effective Landau theory of ferronematics.

An effective Landau-like description of ferronematics, i.e., suspensions of magnetic colloidal particles in a nematic liquid crystal (NLC), is developed in terms of the corresponding magnetization and nematic director fields.

Transient dynamics of electric double-layer capacitors: Exact expressions within the Debye-Falkenhagen approximation.

We revisit a classical problem of theoretical electrochemistry: the response of an electric double-layer capacitor (EDLC) subject to a small, suddenly applied external potential. We solve the Debye-Falkenhagen equation to obtain exact expressions for key EDLC quantities: the ionic charge density, the ionic current density, and the electric field. In contrast to earlier works, our results are not restricted to the long-time asymptotics of those quantities.

Electrostatic interaction between dissimilar colloids at fluid interfaces.

The electrostatic interaction between two nonidentical, moderately charged colloids situated in close proximity of each other at a fluid interface is studied. By resorting to a well-justified model system, this problem is analytically solved within the framework of linearized Poisson-Boltzmann density functional theory. The resulting interaction comprises a surface and a line part, both of which, as functions of the interparticle separation, show a rich behavior including monotonic as well as nonmonotonic variations.

Electrolyte solutions at heterogeneously charged substrates.

The influence of a chemically or electrically heterogeneous distribution of interaction sites at a planar substrate on the number density of an adjacent fluid is studied by means of classical density functional theory (DFT). In the case of electrolyte solutions the effect of this heterogeneity is particularly long ranged, because the corresponding relevant length scale is set by the Debye length which is large compared to molecular sizes. The DFT used here takes the solvent particles explicitly into account and thus captures phenomena, inter alia, due to ion-solvent coupling.

Local pressure for confined systems.

We derive a general closed expression for the local pressure exerted onto the corrugated walls of a channel confining a fluid medium. When the fluid medium is at equilibrium, the local pressure is a functional of the shape of the walls. It is shown that, due to the intrinsic nonlocal character of the interactions among the particles forming the fluid, the applicability of approximate schemes such as the concept of a surface of tension or morphometric thermodynamics is limited to wall curvatures that are small compared to the range of particle-particle interactions.

Wedge wetting by electrolyte solutions.

The wetting of a charged wedgelike wall by an electrolyte solution is investigated by means of classical density functional theory. As in other studies on wedge wetting, this geometry is considered as the most simple deviation from a planar substrate, and it serves as a first step toward more complex confinements of fluids. By focusing on fluids containing ions and surface charges, features of real systems are covered that are not accessible within the vast majority of previous theoretical studies concentrating on simple fluids in contact with uncharged wedges.

Spontaneous symmetry breaking of charge-regulated surfaces.

The interaction between two chemically identical charge-regulated surfaces is studied using the classical density functional theory. In contrast to common expectations and assumptions, under certain realistic conditions we find a spontaneous emergence of disparate charge densities on the two surfaces. The surface charge densities can differ not only in their magnitude, but quite unexpectedly, even in their sign, implying that the electrostatic interaction between the two chemically identical surfaces can be attractive instead of repulsive.

Smectic phases in ionic liquid crystals.

Ionic liquid crystals (ILCs) are anisotropic mesogenic molecules which carry charges and therefore combine properties of liquid crystals, e.g. the formation of mesophases, and of ionic liquids, such as low melting temperatures and tiny triple-point pressures.

Surface induced smectic order in ionic liquids - an X-ray reflectivity study of [CCim][NTf].

Surface induced smectic order was found for the ionic liquid 1-methyl-3-docosylimidazolium bis(trifluoromethlysulfonyl)imide by X-ray reflectivity and grazing incidence scattering experiments. Near the free liquid surface, an ordered structure of alternating layers composed of polar and non-polar moieties is observed. This leads to an oscillatory interfacial profile perpendicular to the liquid surface with a periodicity of 3.

Salt-induced microheterogeneities in binary liquid mixtures.

The salt-induced microheterogeneity (MH) formation in binary liquid mixtures is studied by small-angle x-ray scattering (SAXS) and liquid state theory. Previous experiments have shown that this phenomenon occurs for antagonistic salts, whose cations and anions prefer different components of the solvent mixture. However, so far the precise mechanism leading to the characteristic length scale of MHs has remained unclear.

Electrolyte solutions at curved electrodes. II. Microscopic approach.

Density functional theory is used to describe electrolyte solutions in contact with electrodes of planar or spherical shape. For the electrolyte solutions, we consider the so-called civilized model, in which all species present are treated on equal footing. This allows us to discuss the features of the electric double layer in terms of the differential capacitance.

Electrolyte solutions at curved electrodes. I. Mesoscopic approach.

Within the Poisson-Boltzmann approach, electrolytes in contact with planar, spherical, and cylindrical electrodes are analyzed systematically. The dependences of their capacitance C on the surface charge density σ and the ionic strength I are examined as a function of the wall curvature. The surface charge density has a strong effect on the capacitance for small curvatures, whereas for large curvatures the behavior becomes independent of σ.

Mesoscopic Correlation Functions in Heterogeneous Ionic Liquids.

A common feature of ionic liquids composed of cations with long aliphatic side chains is structural heterogeneities on the nanometer length scale. This so-called microphase separation arises from the clustering of aliphatic moieties. The temperature dependence of the liquid bulk structure was studied by small-angle X-ray and neutron scattering for a set of methylimidazolium ([CCim], [CCim]) based ionic liquids with tris(pentafluoroethyl)trifluorophosphate ([FAP]), bis(trifluoromethylsulfonyl)imide ([NTf]), and bis(nonafluorobutylsulfonyl)imide ([NNf]) anions.

Three-phase contact line and line tension of electrolyte solutions in contact with charged substrates.

The three-phase contact line formed by the intersection of a liquid-vapor interface of an electrolyte solution with a charged planar substrate is studied in terms of classical density functional theory applied to a lattice model. The influence of the substrate charge density and of the ionic strength of the solution on the intrinsic structure of the three-phase contact line and on the corresponding line tension is analyzed. We find a negative line tension for all values of the surface charge density and of the ionic strength considered.