arXiv subjects

Siegfried Dietrich

Publications and source records attributed to Siegfried Dietrich.

At least 19 recordsLinked to original sources

arXiv2024

Structure of liquid--vapor interfaces: perspectives from liquid state theory, large-scale simulations, and potential grazing-incidence X-ray diffraction

Grazing-incidence X-ray diffraction (GIXRD) is a scattering technique which allows one to characterize the structure of fluid interfaces down to the molecular scale, including the measurement of the surface tension and of the interface roughness. However, the corresponding standard data analysis at non-zero wave numbers has been criticized as to be inconclusive because the scattering intensity is polluted by the unavoidable scattering from the bulk. Here we overcome this ambiguity by proposing a physically consistent model of the bulk contribution which is based on a minimal set of assumptions of experimental relevance. To this end, we derive an explicit integral expression for the background scattering, which can be determined numerically from the static structure factors of the coexisting bulk phases as independent input. Concerning the interpretation of GIXRD data inferred from computer simulations, we account also for the finite sizes of the bulk phases, which are unavoidable in simulations. The corresponding leading-order correction beyond the dominant contribution to the scattered intensity is revealed by asymptotic analysis, which is characterized by the competition between the linear system size and the X-ray penetration depth in the case of simulations. Specifically, we have calculated the expected GIXRD intensity for scattering at the planar liquid--vapor interface of Lennard-Jones fluids with truncated pair interactions via extensive, high-precision simulations. The reported data cover interfacial and bulk properties of fluid states along the whole liquid--vapor coexistence line. A sensitivity analysis demonstrates the robustness of our findings concerning the detailed definition of the mean interface position. We conclude that previous claims of an enhanced surface tension at mesoscopic scales are amenable to unambiguous tests via scattering experiments.

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arXiv2020

Finite-size corrections for the static structure factor of a liquid slab with open boundaries

The presence of a confining boundary can modify the local structure of a liquid markedly. In addition, small samples of finite size are known to exhibit systematic deviations of thermodynamic quantities relative to their bulk values. Here, we consider the static structure factor of a liquid sample in slab geometry with open boundaries at the surfaces, which can be thought of as virtually cutting out the sample from a macroscopically large, homogeneous fluid. This situation is a relevant limit for the interpretation of grazing-incidence diffraction experiments at liquid interfaces and films. We derive an exact, closed expression for the slab structure factor, with the bulk structure factor as the only input. This shows that such free boundary conditions cause significant differences between the two structure factors, in particular at small wavenumbers. An asymptotic analysis of this result yields the scaling exponent and an accurate, useful approximation of these finite-size corrections. Furthermore, the open boundaries permit the interpretation of the slab as an open system, supporting particle exchange with a reservoir. We relate the slab structure factor to the particle number fluctuations and discuss conditions under which the subvolume of the slab represents a grand canonical ensemble with chemical potential $μ$ and temperature $T$. Thus, the open slab serves as a test-bed for the small-system thermodynamics in a $μT$ reservoir. We provide a microscopically justified and exact result for the size dependence of the isothermal compressibility. Our findings are corroborated by simulation data for Lennard-Jones liquids at two representative temperatures.

cond-mat.stat-mech↗

arXiv2020

Effective Pair Interaction of Patchy Particles in Critical Fluids

We study the critical Casimir interaction between two spherical colloids immersed in a binary liquid mixture close to its critical demixing point. The surface of each colloid prefers one species of the mixture with the exception of a circular patch of arbitrary size, where the other species is preferred. For such objects we calculate, within the Derjaguin approximation, the scaling function describing the critical Casimir potential, and we use it to derive the scaling functions for all components of the forces and torques acting on both colloids. The results are compared with available experimental data. Moreover, the general relation between the scaling function for the potential and the scaling functions for the force and the torque is derived.

cond-mat.stat-mech↗

arXiv2020

Floor- or ceiling-sliding for chemically active, gyrotactic, sedimenting Janus particles

Surface bound catalytic chemical reactions self-propel chemically active Janus particles. In the vicinity of boundaries, these particles exhibit rich behavior, such as the occurrence of wall-bound steady states of "sliding". Most active particles tend to sediment as they are density mismatched with the solution. Moreover Janus spheres, which consist of an inert core material decorated with a cap-like, thin layer of a catalyst, are gyrotactic ("bottom-heavy"). Occurrence of sliding states near the horizontal walls depends on the interplay between the active motion and the gravity-driven sedimentation and alignment. It is thus important to understand and quantify the influence of these gravity-induced effects on the behavior of model chemically active particles moving near walls. For model gyrotactic, self-phoretic Janus particles, here we study theoretically the occurrence of sliding states at horizontal planar walls that are either below ("floor") or above ("ceiling") the particle. We construct "state diagrams" characterizing the occurrence of such states as a function of the sedimentation velocity and of the gyrotactic response of the particle, as well as of the phoretic mobility of the particle. We show that in certain cases sliding states may emerge simultaneously at both the ceiling and the floor, while the larger part of the experimentally relevant parameter space corresponds to particles that would exhibit sliding states only either at the floor or at the ceiling or there are no sliding states at all. These predictions are critically compared with the results of previous experimental studies and our experiments conducted on Pt-coated polystyrene and silica-core particles suspended in aqueous hydrogen peroxide solutions.

cond-mat.soft↗

arXiv2019

Critical Casimir interaction between colloidal Janus-type particles in two spatial dimensions

We study colloidal particles with chemically inhomogeneous surfaces suspended in a critical binary liquid mixture. The inhomogeneous particle surface is composed of patches with alternating adsorption preferences for the two components of the binary solvent. By describing the binary liquid mixture \emph{at} its consolute point in terms of the critical Ising model we exploit its conformal invariance in two spatial dimension. This allows us to determine exactly the universal profiles of the order parameter, the energy density, and the stress tensor as well as some of their correlation functions around a single particle for various shapes and configurations of the surface patches. The formalism encompasses several interesting configurations, including Janus particles of circular and needle shapes with dipolar symmetry and a circular particle with quadrupolar symmetry. From these single-particle properties we construct the so-called small particle operator expansion (SPOE), which enables us to obtain asymptotically exact expressions for the position- and orientation-dependent critical Casimir interactions of the particles with distant objects, such as another particle or the confining walls of a half plane, strip, or wedge, with various boundary conditions for the order parameter. In several cases we compare the interactions at large distances with the ones at close distance (but still large on the molecular scale). We also compare our analytical results for two Janus particles with recent simulation data.

cond-mat.stat-mech↗

arXiv2018

Ferronematics in confinement

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., the one at which the ferronematic sample becomes distorted) as function of the system parameters can be inferred. Two possible mechanisms of switching the magnetization by applying a magnetic field in the antiparallel direction are observed and characterized in terms of the coupling constant between the magnetization and the nematic director as well as in terms of the coupling strength of the nematic liquid crystal and the walls of the slab. Suitably prepared walls allow one to combine both switching mechanisms in one setup, such that one can construct a cell the magnetization of which can be reversibly switched off.

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arXiv2018

Controlling the dynamics of colloidal particles by critical Casimir forces

Critical Casimir forces can play an important role for applications in nano-science and nanotechnology, owing to their piconewton strength, nanometric action range, fine tunability as a function of temperature, and exquisite dependence on the surface properties of the involved objects. Here, we investigate the effects of critical Casimir forces on the free dynamics of a pair of colloidal particles dispersed in the bulk of a near-critical binary liquid solvent, using blinking optical tweezers. In particular we measure the time evolution of the distance between the two colloids to determine their relative diffusion and drift velocity. Furthermore, we show how critical Casimir forces change the dynamic properties of this two-colloid system by studying the temperature dependence of the distribution of the so-called first-passage time, i.e., of the time necessary for the particles to reach for the first time a certain separation, starting from an initially assigned one. These data are in good agreement with theoretical results obtained from Monte Carlo simulations and Langevin dynamics.

cond-mat.stat-mech↗

arXiv2018

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. The study is based on a microscopic model and on classical density functional theory. Ferronematics are susceptible to weak magnetic fields and they can exhibit a ferromagnetic phase, which has been predicted several decades ago and which has recently been found experimentally. Within the proposed effective Landau theory of ferronematics one has quantitative access, e.g., to the coupling between the magnetization of the magnetic colloids and the nematic director of the NLC. On mesoscopic length scales this generates complex response patterns.

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arXiv2017

Collective behavior of colloids due to critical Casimir interactions

If colloidal solute particles are suspended in a solvent close to its critical point, they act as cavities in a fluctuating medium and thereby restrict and modify the fluctuation spectrum in a way which depends on their relative configuration. As a result effective, so-called critical Casimir forces (CCFs) emerge between the colloids. The range and the amplitude of CCFs depend sensitively on the temperature and the composition of the solvent as well as on the boundary conditions of the order parameter of the solvent at the particle surfaces. These remarkable, moreover universal features of the CCFs provide the possibility for an active control over the assembly of colloids. This has triggered a recent surge of experimental and theoretical interest in these phenomena. We present an overview of current research activities in this area. Various experiments demonstrate the occurrence of thermally reversible self-assembly or aggregation or even equilibrium phase transitions of colloids in the mixed phase below the lower consolute points of binary solvents. We discuss the status of the theoretical description of these phenomena, in particular the validity of a description in terms of effective, one-component colloidal systems and the necessity of a full treatment of a ternary solvent-colloid mixture. We suggest perspectives on the directions towards which future research in this field might develop.

cond-mat.soft↗

arXiv2017

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. Previous density functional calculations have revealed that the phase behavior of ILCs is strongly affected by their molecular properties, i.e., their aspect ratio, the loci of the charges, and their interaction strengths. Here, we report new findings concerning the phase behavior of ILCs as obtained by density functional theory and Monte Carlo simulations. The most important result is the occurrence of a novel, wide smectic-A phase $S_{AW}$, at low temperature, the layer spacing of which is larger than that of the ordinary high-temperature smectic-A phase $S_{A}$. Unlike the ordinary smectic $S_A$ phase, the structure of the $S_{AW}$ phase consists of alternating layers of particles oriented parallel to the layer normal and oriented perpendicular to it.

cond-mat.soft↗

arXiv2016

Tricritical Casimir forces and order parameter profiles in wetting films of $^3\text{He}$ -$^4\text{He}$ mixtures

Tricritical Casimir forces in $^3\text{He}$ -$^4\text{He}$ wetting films are studied, within mean field theory, in therms of a suitable lattice gas model for binary liquid mixtures with short--ranged surface fields. The proposed model takes into account the continuous rotational symmetry O(2) of the superfluid degrees of freedom associated with $^4\text{He}$ and it allows, inter alia, for the occurrence of a vapor phase. As a result, the model facilitates the formation of wetting films, which provides a strengthened theoretical framework to describe available experimental data for tricritical Casimir forces acting in $^3\text{He}$ -$^4\text{He}$ wetting films.

cond-mat.stat-mech↗

arXiv2016

Critical Casimir forces between defects in the 2D Ising model

An exact statistical mechanical derivation is given of the critical Casimir interactions between two defects in a planar lattice-gas Ising model. Each defect is a group of nearest-neighbor spins with modified coupling constants. Such a system can be regarded as a model of a binary liquid mixture with the molecules confined to a membrane and the defects mimicking protein inclusions embedded into the membrane. As suggested by recent experiments, certain cellular membranes appear to be tuned to the proximity of a critical demixing point belonging to the two-dimensional Ising universality class. Therefore one can expect the emergence of critical Casimir forces between membrane inclusions. These forces are governed by universal scaling functions, which we derive for simple defects. We prove that the scaling law appearing at criticality is the same for all types of defects considered here.

cond-mat.stat-mech↗

arXiv2016

Wetting hysteresis induced by nanodefects

Wetting of actual surfaces involves diverse hysteretic phenomena stemming from ever-present imperfections. Here we clarify the origin of wetting hysteresis for a liquid front advancing or receding across an isolated defect of nanometric size. Various kinds of chemical and topographical nanodefects are investigated which represent salient features of actual heterogeneous surfaces. The most probable wetting path across surface heterogeneities is identified by combining, within an innovative approach, microscopic classical density functional theory and the string method devised for the study of rare events. The computed rugged free energy landscape demonstrates that hysteresis emerges as a consequence of metastable pinning of the liquid front at the defects; the barriers for thermally activated defect crossing, the pinning force, and hysteresis are quantified and related to the geometry and chemistry of the defects allowing for the occurrence of nanoscopic effects. The main result of our calculations is that even weak nanoscale defects, which are difficult to characterize in generic microfluidic experiments, can be the source of a plethora of hysteretical phenomena, including the pinning of nanobubbles.

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arXiv2015

Effective interaction between active colloids and fluid interfaces induced by Marangoni flows

We show theoretically that near a fluid-fluid interface a single active colloidal particle generating, e.g., chemicals or a temperature gradient experiences an effective force of hydrodynamic origin. This force is due to the fluid flow driven by Marangoni stresses induced by the activity of the particle; it decays very slowly with the distance from the interface, and can be attractive or repulsive depending on how the activity modifies the surface tension. We show that, for typical systems, this interaction can dominate the dynamics of the particle as compared to Brownian motion, dispersion forces, or self-phoretic effects. In the attractive case, the interaction promotes the self-assembly of particles into a crystal-like monolayer at the interface.

cond-mat.soft↗

arXiv2015

Nonadditivity of Critical Casimir Forces

In soft and condensed matter physics, effective interactions often emerge as a result of the spatial confinement of a fluctuating field. For instance, microscopic particles in a binary liquid mixture are subject to critical Casimir forces whenever their surfaces confine the thermal fluctuations of the order parameter of this kind of solvent, the range of which diverges upon approaching the critical demixing point. Critical Casimir forces are predicted to be nonadditive on a particular large scale. However, a direct experimental evidence of this fact is still lacking. Here, we fill in this gap by reporting the experimental measurement of the associated many-body effects. In particular, we focus on three colloidal particles in optical traps and observe that the critical Casimir force exerted on one of them by the other two colloids differs from the sum of the forces they exert separately. The magnitude and range of this three-body effect turn out to depend sensitively on the distance from the critical point of the solvent and on the preferential adsorption at the surfaces of the colloids for the two components of the mixture.

cond-mat.soft↗

arXiv2014

Effective interaction between a colloid and a soft interface near criticality

Within mean-field theory we determine the universal scaling function for the effective force acting on a single colloid located near the interface between two coexisting liquid phases of a binary liquid mixture close to its critical consolute point. This is the first study of critical Casimir forces emerging from the confinement of a fluctuating medium by at least one soft interface, instead by rigid walls only as studied previously. For this specific system, our semi-analytical calculation illustrates that knowledge of the colloid-induced, deformed shape of the interface allows one to accurately describe the effective interaction potential between the colloid and the interface. Moreover, our analysis demonstrates that the critical Casimir force involving a deformable interface is accurately described by a universal scaling function, the shape of which differs from that one for rigid walls.

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arXiv2013

Nonequilibrium critical Casimir interactions in binary fluids

Colloids immersed in a critical binary liquid mixture are subject to critical Casimir forces (CCFs) because they confine its concentration fluctuations and influence the latter via effective surface fields. To date, CCFs have only been studied in thermodynamic equilibrium. However, due to the critical slowing down, the order parameter around a particle can easily be perturbed by any motion of the colloid or by solvent flow. This leads to significant but largely unexplored changes in the CCF. Here we study the drag force on a single colloidal particle moving in a near-critical fluid mixture and the relative motion of two colloids due to the CCF acting on them. In order to account for the kinetic couplings among the order parameter field, the solvent velocity field, and the particle motion, we use a fluid particle dynamics method. These studies extend the understanding of CCFs from thermal equilibrium to non-equilibrium processes, which are relevant to current experiments, and show the emergence of significant effects near the critical point.

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arXiv2011

Mesoscopic analysis of Gibbs' criterion for sessile nanodroplets on trapezoidal substrates

By taking into account precursor films accompanying nanodroplets on trapezoidal substrates we show that on a mesoscopic level of description one does not observe the phenomenon of liquid-gas-substrate contact line pinning at substrate edges. This phenomenon is present in a macroscopic description and leads to non-unique contact angles which can take values within a range determined by the so-called Gibbs' criterion. Upon increasing the volume of the nanodroplet the apparent contact angle evaluated within the mesoscopic approach changes continuously between two limiting values fulfilling Gibbs' criterion while the contact line moves smoothly across the edge of the trapezoidal substrate. The spatial extent of the range of positions of the contact line, corresponding to the variations of the contact angle between the values given by Gibbs' criterion, is of the order of ten fluid particle diameters.

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