Confined fluids display complex behavior due to layering and local packing. Here, we disentangle these effects by confining a hard-sphere fluid to the surface of a cylinder, such the circumference extends only over a few particle diameters. We compare the static structure factor and the pressure measured in computer simulations to the Percus-Yevick closure in liquid state theory. A non-monotonic evolution of the static-structure-factor peak and the pressure is observed upon variation of the confining length, similar to a liquid confined between two plates. This indicates that the density profile and the particle correlations may not be intrinsically connected in real confined liquids.
The complex behavior of confined fluids arising due to a competition between layering and local packing can be disentangled by considering quasi-confined liquids, where periodic boundary conditions along the confining direction restore translational invariance. This system provides a means to investigate the interplay of the relevant length scales of the confinement and the local order. We provide a mode-coupling theory of the glass transition (MCT) for quasi-confined liquids and elaborate an efficient method for the numerical implementation. The nonergodicity parameters in MCT are compared to…
We investigate the ground state of a classical two-dimensional system of hard-sphere dipoles confined between two hard walls. Using lattice sum minimization techniques we reveal that at fixed wall separations, a first-order transition from a vacuum to a straight one-dimensional chain of dipoles occurs upon increasing the density. Further increase in the density yields the stability of an undulated chain as well as nontrivial buckling structures. We explore the close-packed configurations of dipoles in detail, and we find that, in general, the densest packings of dipoles possess complex magneti…
Disordered jammed packings under confinement have received considerably less attention than their \textit{bulk} counterparts and yet arise in a variety of practical situations. In this work, we study binary sphere packings that are confined between two parallel hard planes, and generalize the Torquato-Jiao (TJ) sequential linear programming algorithm [Phys. Rev. E {\bf 82}, 061302 (2010)] to obtain putative maximally random jammed (MRJ) packings that are exactly isostatic with high fidelity over a large range of plane separation distances $H$, small to large sphere radius ratio $α$ and small s…
We show that hard spheres confined between two parallel hard plates pack denser with periodic adaptive prismatic structures which are composed of alternating prisms of spheres. The internal structure of the prisms adapts to the slit height which results in close packings for a range of plate separations, just above the distance where three intersecting square layers fit exactly between the plates. The adaptive prism phases are also observed in real-space experiments on confined sterically stabilized colloids and in Monte Carlo simulations at finite pressure.
The inherent structure landscape for a system of hard spheres confined to a hard cylindrical channel, such that spheres can only contact their first and second neighbours, is studied using an analytical model that extends previous results [Phys. Rev. Lett. 115, 025702 (2015)] to provide a comprehensive picture of jammed packings over a range of packing densities. In the model, a packing is described as an arrangement of $k$ helical sections, separated by defects, that have alternating helical twist directions and where all spheres satisfy local jamming constraints. The structure of each helica…
We use a series of molecular dynamics simulations, and analytical theory, to demonstrate that a system of hard spheres confined to a narrow cylindrical channel exhibits a continuous phase transition from an isotropic fluid at low densities, to an orientationally ordered, but translationally disordered, helical fluid at high densities. The ordered fluid phase contains small sections of helix separated by topological defects that change the direction of the twist, altering the local chirailty. The defects break up the translational order, but the fluid develops long range orientational order. An…
We report the observation of the homogenous nucleation of crystals in a dense layer of steel spheres confined between two horizontal plates vibrated vertically. Above a critical vibration amplitude, two-layer crystals with square symmetry were found to coexist in steady state with a surrounding granular liquid. By analogy to equilibrium hard sphere systems, the phase behavior can be explained through entropy maximization. However, dramatic non-equilibrium effects are present, including a significant difference in the granular temperatures of the two phases.
Hard-sphere fluids confined between parallel plates a distance $D$ apart are studied for a wide range of packing fractions, including also the onset of crystallization, applying Monte Carlo simulation techniques and density functional theory. The walls repel the hard spheres (of diameter $σ$) with a Weeks-Chandler-Andersen (WCA) potential $V_{WCA}(z) = 4 ε[(σ_w/z)^{12}-(σ_w/z)^6 + 1/4]$, with range $σ_w = σ/2$. We vary the strength $ε$ over a wide range and the case of simple hard walls is also treated for comparison. By the variation of $ε$ one can change both the surface excess packing fract…
We study the phase behavior of hard spheres confined between two parallel hard plates using extensive computer simulations. We determine the full equilibrium phase diagram for arbitrary densities and plate separations from one to five hard-sphere diameters using free energy calculations. We find a first-order fluid-solid transition, which corresponds to either capillary freezing or melting depending on the plate separation. The coexisting solid phase consists of crystalline layers with either triangular or square symmetry. Increasing the plate separation, we find a sequence of crystal structur…
Studies of random close packing of spheres have advanced our knowledge about the structure of systems such as liquids, glasses, emulsions, granular media, and amorphous solids. When these systems are confined their structural properties change. To understand these changes we study random close packing in finite-sized confined systems, in both two and three dimensions. Each packing consists of a 50-50 binary mixture with particle size ratio 1.4. The presence of confining walls significantly lowers the overall maximum area fraction (or volume fraction in three dimensions). A simple model is pres…
We use virial series to study the equilibrium properties of confined soft-spheres fluids interacting through the inverse-power potentials. The confinement is induced by hard walls with planar, spherical and cylindrical shapes. We evaluate analytically the coefficients of order two in density of the wall-fluid surface tension $γ$ and analyze the curvature contributions to the free energy. Emphasis is in bending and Gaussian rigidities, which are found analytically at order two in density. Their contribution to $γ(R)$ and the accuracy of different truncation procedures to the low curvature expan…
We investigate the tagged-particle motion in a strongly interacting quasi-confined liquid using periodic boundary conditions along the confining direction. Within a mode-coupling theory of the glass transition (MCT) we calculate the self-nonergodicity parameters and the self-intermediate scattering function and compare them with event-driven molecular dynamics simulations. We observe non-monotonic behavior for the in-plane mean-square displacement and further correlation functions which refer to higher mode indices encoding information about the perpendicular motion. The in-plane velocity-auto…
Pair distributions of fluids confined between two surfaces at close distance are of fundamental importance for a variety of physical, chemical, and biological phenomena, such as interactions between macromolecules in solution, surface forces, and diffusion in narrow pores. However, in contrast to bulk fluids, properties of inhomogeneous fluids are seldom studied at the pair-distribution level. Motivated by recent experimental advances in determining anisotropic structure factors of confined fluids, we analyze theoretically the underlying anisotropic pair distributions of the archetypical hard-…
Numerical solutions of the mode-coupling theory (MCT) equations for a hard-sphere fluid confined between two parallel hard walls are elaborated. The governing equations feature multiple parallel relaxation channels which significantly complicate their numerical integration. We investigate the intermediate scattering functions and the susceptibility spectra close to structural arrest and compare to an asymptotic analysis of the MCT equations. We corroborate that the data converge in the $β$-scaling regime to two asymptotic power laws, viz. the critical decay and the von Schweidler law. The nume…
We consider a set of identical mobile point-like charges (counter-ions) confined to a domain with curved hard walls carrying a uniform fixed surface charge density, the system as a whole being electroneutral. Three domain geometries are considered: a pair of parallel plates, the cylinder and the sphere. The particle system in thermal equilibrium is assumed to be described by the nonlinear Poisson-Boltzmann theory. While the effectively 1D plates and the 2D cylinder have already been solved, the 3D sphere problem is not integrable. It is shown that the contact density of particles at the charge…
We use grand canonical transition-matrix Monte Carlo and discontinuous molecular dynamics simulations to generate precise thermodynamic and kinetic data for the equilibrium hard-sphere fluid confined between smooth hard walls. These simulations show that the pronounced inhomogeneous structuring of the fluid normal to the confining walls, often the primary focus of density functional theory studies, has a negligible effect on many of its average properties over a surprisingly broad range of conditions. We present one consequence of this insensitivity to confinement: a simple analytical equation…
We study the rheology of confined suspensions of neutrally buoyant rigid monodisperse spheres in plane-Couette flow using Direct Numerical Simulations. We find that if the width of the channel is a (small) integer multiple of the sphere's diameter, the spheres self-organize into two-dimensional layers that slide on each other and the suspension's effective viscosity is significantly reduced. Each two-dimensional layer is found to be structurally liquid-like but their dynamics is frozen in time.
We develop the scaled particle theory to describe the thermodynamic properties and orientation ordering of a binary mixture of hard spheres (HS) and hard spherocylinders (HSC) confined in a disordered porous medium. Using this theory the analytical expressions of the free energy, the pressure and the chemical potentials of HS and HSC have been derived. The improvement of obtained results is considered by introducing the Carnahan-Starling-like and Parsons-Lee-like corrections. Phase diagrams for the isotropic-nematic transition are calculated from the bifurcation analysis of the integral equati…
By means of numerical simulations, we study the influence of confinement on three-dimensional random close packed (RCP) granular materials subject to gravity. The effects of grain shape (spherical or polyhedral) and polydispersity on this dependence are investigated. In agreement with a simple geometrical model, the solid fraction is found to decrease linearly for increasing confinement no matter the grain shape. This decrease remains valid for bidisperse sphere packings although the gradient seems to reduce significantly when the proportion of small particles reaches 40% by volume. The aforem…
Within a recently developed mode-coupling theory for fluids confined to a slit we elaborate numerical results for the long-time limits of suitably generalized intermediate scattering functions. The theory requires as input the density profile perpendicular to the plates, which we obtain from density functional theory within the fundamental-measure framework, as well as symmetry-adapted static structure factors which can be calculated relying on the inhomogeneous Percus-Yevick closure. Our calculations for the nonergodicity parameters for both the collective as well as for the self motion are i…
Glass forming liquids exhibit a rich phenomenology upon confinement. This is often related to the effects arising from wall-fluid interactions. Here we focus on the interesting limit where the separation of the confining walls becomes of the order of a few particle diameters. For a moderately polydisperse, densely packed hard-sphere fluid confined between two smooth hard walls, we show via event-driven molecular dynamics simulations the emergence of a multiple reentrant glass transition scenario upon a variation of the wall separation. Using thermodynamic relations, this reentrant phenomenon i…
Although density functional theory provides reliable predictions for the static properties of simple fluids under confinement, a theory of comparative accuracy for the transport coefficients has yet to emerge. Nonetheless, there is evidence that knowledge of how confinement modifies static behavior can aid in forecasting dynamics. Specifically, molecular simulation studies have shown that the relationship between excess entropy and self diffusivity of a bulk equilibrium fluid changes only modestly when the fluid is isothermally confined, indicating that knowledge of the former might allow semi…
Stochastic simulations are used to characterize the knotting distributions of random ring polymers confined in spheres of various radii. The approach is based on the use of multiple Markov chains and reweighting techniques, combined with effective strategies for simplifying the geometrical complexity of ring conformations without altering their knot type. By these means we extend previous studies and characterize in detail how the probability to form a given prime or composite knot behaves in terms of the number of ring segments, $N$, and confining radius, $R$. For $ 50 \le N \le 450 $ we show…
In this work, the local pressure of fluids confined inside nanoslit pores is predicted within the framework of the density functional theory. The Euler-Lagrange equation in the density functional theory of statistical mechanics is used to obtain the force balance equation which leads to a general equation to predict the local normal component of the pressure tensor. Our approach yields a general equation for predicting the normal pressure of confined fluids and it satisfies the exact bulk thermodynamics equation when the pore width approaches infinity. As two basic examples, we report the solu…
Mechanical impulse propagation in granular media depends strongly on the imposed confinement conditions. In this work, the propagation of sound in a granular packing contained by flexible walls that enable confinement under hydrostatic pressure conditions is investigated. This configuration also allows the form of the input impulse to be controlled by means of an instrumented impact pendulum. The main characteristics of mechan- ical wave propagation are analyzed, and it is found that the wave speed as function of the wave amplitude of the propagating pulse obeys the predictions of the Hertz co…
We study the conformations of a semiflexible chain, confined in nano-scaled spherical cavities, under two distinct processes of confinement. Radial contraction and packaging are employed as two confining procedures. The former method is performed by gradually decreasing the diameter of a spherical shell which envelopes a confined chain. The latter procedure is carried out by injecting the chain inside a spherical shell through a hole on the shell surface. The chain is modeled with a rigid body molecular dynamics simulation and its parameters are adjusted to DNA base-pair elasticity. Directiona…
We develop an analytical method for studying the properties of a non-interacting Wormlike Chain (WLC) in confined geometries. The mean field-like theory replaces the rigid constraints of confinement with average constraints, thus allowing us to develop a tractable method for treating a WLC wrapped on the surface of a sphere, and fully encapsulated within it. The efficacy of the theory is established by reproducing the exact correlation functions for a WLC confined to the surface of a sphere. In addition, the coefficients in the free energy are exactly calculated. We also describe the behavior …
We investigate confined shear thickening suspensions for which the sample thickness is comparable to the particle dimensions. Rheometry measurements are presented for densely packed suspensions of spheres and rods with aspect ratios 6 and 9. By varying the suspension thickness in the direction of the shear gradient at constant shear rate, we find pronounced oscillations in the stress. These oscillations become stronger as the gap size is decreased, and the stress is minimized when the sample thickness becomes commensurate with an integer number of particle layers. Despite this confinement-indu…
The motion of an optically trapped sphere constrained by the vicinity of a wall is investigated at times where hydrodynamic memory is significant. First, we quantify, in bulk, the influence of confinement arising from the trapping potential on the sphere's velocity autocorrelation function $C(t)$. Next, we study the splitting of $C(t)$ into $C_\parallel(t)$ and $C_\perp(t)$, when the sphere is approached towards a surface. Thereby, we monitor the crossover from a slow $t^{-3/2}$ long-time tail, away from the wall, to a faster $t^{-5/2}$ decay, due to the subtle interplay between hydrodynamic b…
The bending energy of any freely deformable closed surface is quadratic in its curvature. In the absence of constraints, it will be minimized when the surface adopts the form of a round sphere. If the surface is confined within a hypersurface of smaller size, however, this spherical state becomes inaccessible. A framework is introduced to describe the equilibrium states of the confined surface. It is applied to a two-dimensional surface confined within a three-dimensional hypersphere of smaller radius. If the excess surface area is small, the equilibrium states are represented by harmonic defo…
We study the diffusive dynamics of a hard-sphere fluid confined between parallel smooth hard walls. The position-dependent diffusion coefficient normal to the walls is larger in regions of high local packing density. High density regions also have the largest available volume, consistent with the fast local diffusivity. Indeed, local and global diffusivities as a function of the Widom insertion probability approximately collapse onto a master curve. Parallel and average normal diffusivities are strongly coupled at high densities and deviate from bulk fluid behavior.
Using event-driven molecular dynamics simulations, we quantify how the self diffusivity of confined hard-sphere fluids depends on the nature of the confining boundaries. We explore systems with featureless confining boundaries that treat particle-boundary collisions in different ways and also various types of physically (i.e., geometrically) rough boundaries. We show that, for moderately dense fluids, the ratio of the self diffusivity of a rough wall system to that of an appropriate smooth-wall reference system is a linear function of the reciprocal wall separation, with the slope depending on…
Charge-stabilized colloidal spheres dispersed in weak 1:1 electrolytes are supposed to repel each other. Consequently, experimental evidence for anomalous long-ranged like-charged attractions induced by geometric confinement inspired a burst of activity. This has largely subsided because of nagging doubts regarding the experiments' reliability and interpretation. We describe a new class of thermodynamically self-consistent colloidal interaction measurements that confirm the appearance of pairwise attractions among colloidal spheres confined by one or two bounding walls. In addition to supporti…
We use analytical calculations and event-driven molecular dynamics simulations to study a small number of hard sphere particles in a spherical cavity. The cavity is taken also as the thermal bath so that the system thermalizes by collisions with the wall. In that way, these systems of two, three and four particles, are considered in the canonical ensemble. We characterize various mean and thermal properties for a wide range of number densities. We study the density profiles, the components of the local pressure tensor, the interface tension, and the adsorption at the wall. This spans from the …
We study by Monte Carlo simulation a binary mixture of neutral and dipolar hard-spheres with non-additive diameters. With a view to understanding the interplay between population inversion for an open pore and the demixing phase transitions, the mixture is considered in the bulk and confined between two parallel hard-walls modeling a slit pore. A uniform field is applied in the pore in order to control its composition as shown previously. The demixing lines in the bulk and in the pore are studied by the Gibbs Ensemble Monte Carlo method. The open pore-bulk mixture equilibrium is studied by a c…
We use discontinuous molecular dynamics and grand-canonical transition-matrix Monte Carlo simulations to explore how confinement between parallel hard walls modifies the relationships between packing fraction, self-diffusivity, partial molar excess entropy, and total excess entropy for binary hard-sphere mixtures. To accomplish this, we introduce an efficient algorithm to calculate partial molar excess entropies from the transition-matrix Monte Carlo simulation data. We find that the species-dependent self-diffusivities of confined fluids are very similar to those of the bulk mixture if compar…
We investigate the tight packing of nematic polymers inside a confining hard sphere. We model the polymer {\sl via} the continuum Frank elastic free energy augmented by a simple density dependent part as well as by taking proper care of the connectivity of the polymer chains when compared with simple nematics. The free energy {\sl ansatz} is capable of describing an orientational ordering transition within the sample between an isotropic polymer solution and a polymer nematic phase. We solve the Euler-Lagrange equations numerically with the appropriate boundary conditions for the director and …
We analyze static properties of a strongly confined semiflexible polymer, i.e. either trapped in a closed space or compressed by external forces, in an athermal solvent. Like a flexible polymer case, we can resort to an analogy with the semidilute solution, but a complication due to the additional length scale arising from the chain rigidity results in more diverse behaviours depending on system parameters. For each regime, scaling forms of the excess free energy of the confinement are derived. Effects of the confinement geometry and the solvent quality are briefly discussed.
This work is devoted to the exact statistical mechanics treatment of simple inhomogeneous few-body systems. The system of two Hard Spheres (HS) confined in a hard spherical pore is systematically analyzed in terms of its dimensionality >. The canonical partition function, and the one- and two-body distribution functions are analytically evaluated and a scheme of iterative construction of the system properties is presented. We analyse in detail both the effect of high confinement, when particles become caged, and the low density limit. Other confinement situations are also studied analytically …
Using agent-based simulations of self-propelled particles subject to short-range repulsion and nematic alignment we explore the dynamical phases of a dense active material confined to the surface of a sphere. We map the dynamical phase diagram as a function of curvature, alignment strength and activity and reproduce phases seen in recent experiments on active microtubules moving on the surfaces of vesicles. At low driving, we recover the equilibrium nematic ground state with four +1/2 defects. As the driving is increased, geodesic forces drive the transition to a band of polar matter wrapping …
Dynamical properties of a Lennard-Jones binary mixture embedded in an off lattice matrix of soft spheres are studied in the direct space upon supercooling by molecular dynamics simulations. On lowering temperature the smaller particles tend to avoid the soft sphere interfaces and correspondingly their mobility decreases below the one of the larger particles. The system displays a dynamic behaviour consistent with the Mode Coupling predictions. A decrease of the mode coupling crossover temperature with respect to the bulk is found. We find however that the range of validity of the theory shrink…
Recent theories predict that when a supercooled liquid approaches the glass transition, particle clusters with a special "amorphous order" nucleate within the liquid, which lead to static correlations dictating the dramatic slowdown of liquid relaxation. The prediction, however, has yet to be verified in 3D experiments. Here, we design a colloidal system, where particles are confined inside spherical cavities with an amorphous layer of particles pinned at the boundary. Using this novel system, we capture the amorphous-order particle clusters and demonstrate the development of a static correlat…
Quasi-two-dimensional (quasi-2D) colloidal hard-sphere suspensions confined in a slit geometry are widely used as two dimensional (2D) model systems in experiments that probe the glassy relaxation dynamics of 2D systems. However, the question to what extent these quasi-2D systems indeed represent 2D systems is rarely brought up. Here, we use computer simulations that take into account hydrodynamic interactions to show that dense quasi-2D colloidal bi-disperse hard-sphere suspensions exhibit much more rapid diffusion and relaxation than their 2D counterparts at the same area fraction. This diff…
The transmission rules of interparticle forces between granular particles were analyzed, and a discrete packing model was proposed to calculate the static pressure at the bottom of granular material confined in a vertical column. The mechanical analysis and numerical simulation results indicate that the silo effect is caused by the frictional contacts between border particles and inner walls, the static pressure at the bottom depends on the external load initially, and then tends to a saturation pressure (Pn) in an exponential form. The saturation pressure (Pn) is positive linear related to th…
Extending mode-coupling theory, we elaborate a microscopic theory for the glass transition of liquids confined between two parallel flat hard walls. The theory contains the standard MCT equations in bulk and in two dimensions as limiting cases and requires as input solely the equilibrium density profile and the structure factors of the fluid in confinement. We evaluate the phase diagram as a function of the distance of the plates for the case of a hard sphere fluid and obtain an oscillatory behavior of the glass transtion line as a result of the structural changes related to layering.
Despite the ubiquitousness and technological and scientific importance of granular matter, our understanding is still very poor compared to molecular fluids and solids. Until today, there is no unified description, which indeed seems unreachable. However, it has been proposed that important advances could be attained for noncohesive, hard-sphere like systems, by combining fluid dynamics with phase-field modeling through an appropriate order parameter (Aranson and Tsimring, 2006). Here, we present a review of the dynamics of confined granular matter, for which this systematic approach has prove…
We show that the dynamics of soft-sphere systems with purely repulsive interactions can be described by introducing an effective hard-sphere diameter determined using the Andersen-Weeks-Chandler approximation. We find that this approximation, known to describe static properties of liquids, also gives a good description of a dynamical quantity, the relaxation time, even in the vicinity of the glass transition.
We report a detailed experimental study of the structure and dynamics of glassy states in hard spheres with short-range attraction. The system is a suspension of nearly-hard-sphere colloidal particles and non-adsorbing linear polymer which induces a depletion attraction between the particles. Observation of crystallization reveals a re-entrant glass transition. Static light scattering shows a continuous change in the static structure factors upon increasing attraction. Dynamic light scattering results, which cover 11 orders of magnitude in time, are consistent with the existence of two distinc…
We present a method to filter a distribution so that it is confined within a sphere of given radius r_c and, simultaneously, whose Fourier transform is optimally confined within a sphere of radius k_c. Our procedure may have several applications in the field of electronic structure methods, like the generation of optimized pseudopotentials and localized pseudocore charge distributions. As an example, we describe a particular application within the SIESTA method for density functional calculations, in removing the spurious rippling of the energy surface generated by the integrations in a real s…
The thermodynamic properties of disks moving in a channel sufficiently narrow that they can collide only with their nearest neighbors can be solved exactly by determining the eigenvalues and eigenfunctions of an integral equation. Using it we have determined the correlation length $ξ$ of this system. We have developed an approximate solution which becomes exact in the high density limit. It describes the system in terms of defects in the regular zigzag arrangement of disks found in the high-density limit. The correlation length is then effectively the spacing between the defects. The time scal…
