We examine the ordering properties of rectangular hard rods with length L and diameter D at a single planar wall and between two parallel hard walls using the second-virial density functional theory. The theory is implemented in the three-state Zwanzig approximation, where only three mutually perpendicular directions are allowed for the orientations of hard rods. The effect of varying shape anisotropy is examined at L/D=10, 15 and 20. In contact with a single hard wall, the density profiles show planar ordering, damped oscillatory behavior, and wall induced surface ordering transition below the coexisting isotropic density of bulk isotropic-nematic (I-N) phase transition. Upon approaching the coexisting isotropic density, the thickness of nematic film diverges logarithmically, i.e. the nematic wetting is complete for any shape anisotropy. In the case of confinement between two parallel hard walls, it is found that the continuous surface ordering transition depends strongly on the distance between confining walls (H) for H<L, while it depends weakly on H for H>L. The minimal density at which a surface ordering transition can be realized is located at around H~2D for all studied shape anisotropies due to the strong interference effect between the two hard walls. The first order I-N phase transition of the bulk system becomes surface ordered isotropic (IB)-capillary nematic (NB) phase transition in the slit pore. This first order IB-NB transition weakens with decreasing pore width and terminates in a critical point for all studied shape anisotropies.
We use the Parsons Lee modification of Onsagers second virial theory within the restricted orientation approximation to analyse the phase behaviour of hard cylindrical rods confined in narrow pores Depending on the wall to wall separation we predict a number of distinctly different surface generated nematic phases including a biaxial planar nematic with variable number of layers a monolayer homeotropic and a hybrid T type structure For narrow pores we find evidence of two types of second order uniaxial biaxial transitions depending on the aspect ratio of the particles More specifically we obse…
Density-functional theory is used to investigate the phase behavior of colloidal binary hard-platelet and hard-rod fluids near a single hard wall or confined in a slit pore. The Zwanzig model, in which the orientations of the particles of rectangular shape are restricted to three orthogonal orientations, is analyzed by numerical minimization of the grand potential functional. The density and orientational profiles as well as the surface contributions to the grand potential are determined. The calculations exhibit a wall-induced continuous surface transition from uniaxial to biaxial symmetry fo…
Orientational ordering driven by mechanical distortion of soft substrates plays a major role in material transformation processes such as elastocapillarity and surface anchoring. We present a theoretical model of the orientational response of anisotropic rods deposited onto a surface of a soft, elastic substrate of finite thickness. We show that anisotropic rods exhibit a continuous isotropic-nematic phase transition, driven by orientational interactions between surface deposited rods. This interaction is mediated by the deformation of the underlying elastic substrate, and is quantified by the…
Based on Monte Carlo (MC) computer simulations we study the structure formation of a system of magnetic nanorods. Our model particles consist of fused spheres with permanent magnetic dipole moments, as inspired by recent experiments. The resulting system behaves significantly different from a system of hard (non-magnetic) rods or magnetic rods with a single longitudinal dipole. In particular, we observe for the magnetic nanorods a significant decrease of the percolation threshold (as compared to non-magnetic rods) at low densities, and a stabilization of the high-density nematic phase. Moreove…
We derive a model describing spatio-temporal organization of an array of microtubules interacting via molecular motors. Starting from a stochastic model of inelastic polar rods with a generic anisotropic interaction kernel we obtain a set of equations for the local rods concentration and orientation. At large enough mean density of rods and concentration of motors, the model describes orientational instability. We demonstrate that the orientational instability leads to the formation of vortices and (for large density and/or kernel anisotropy) asters seen in recent experiments.
In order to investigate the coupling between the degrees of alignment of elongated particles in binary nematic dispersions, surfactant stabilized single-wall carbon nanotubes (CNTs) have been added to nematic suspensions of colloidal rodlike viruses in aqueous solution.We have independently measured the orientational order parameter of both components of the guest-host system by means of polarized Raman spectroscopy and by optical birefringence, respectively. Our system allows us therefore to probe the regime where the guest particles (CNTs) are shorter and thinner than the fd virus host parti…
The long range attractive force between two hydrophobic surfaces immersed in water is observed to decrease exponentially with their separation -- this distance-dependence of effective force is known as the hydrophobic force law (HFL). We explore the microscopic origin of HFL by studying distance-dependent attraction between two parallel rods immersed in 2D Mercedes Benz model of water. This model is found to exhibit a well-defined HFL. Although the phenomenon is conventionally explained by density-dependent theories, we identify orientation, rather than density, as the relevant order parameter…
I study the effect of length polydispersity in the surface phase diagram of hard rods interacting with a hard wall. The properly extended interface Gibbs-Duhem equation for a polydisperse system allows us to predict the behaviour of the surface tension as a function of the bulk density at the the wall-isotropic interface. Two groups of qualitative different bulk and surface phase diagrams are calculated from two families of parametrized length distribution functions $p(l)$. This parameterization controls the law of decay at large $l$. I also study the segregation due to polydispersity at the i…
There is now convincing evidence that inter-particle frictional contacts are essential for observing shear-thickening in concentrated suspensions of compact particles. While this has inspired many strategies to tailor the rheology in these systems, in the more general case, viz-a-viz suspensions of anisotropic particles, the mechanism of shear-thickening remains unclear. Here through simultaneous measurements of the bulk viscosity and the first Normal stress difference, we show that strong shear thickening in suspensions of colloidal rods is accompanied by large positive normal stresses, indic…
Motivated by experiments on colloidal membranes composed of chiral rod-like viruses, we use Monte Carlo methods to determine the phase diagram for the liquid crystalline order of the rods and the membrane shape. We generalize the Lebwohl-Lasher model for a nematic with a chiral coupling to a curved surface with edge tension and a resistance to bending, and include an energy cost for tilting of the rods relative to the local membrane normal. The membrane is represented by a triangular mesh of hard beads joined by bonds, where each bead is decorated by a director. The beads can move, the bonds c…
It is known from grand canonical simulations of a system of hard rods on two dimensional lattices that an orientationally ordered nematic phase exists only when the length of the rods is at least seven. However, a recent microcanonical simulation with diffusion kinetics, conserving both total density and zero nematic order, reported the existence of a nematically phase segregated steady state with interfaces in the diagonal direction for rods of length six [Phys. Rev. E 95, 052130 (2017)], violating the equivalence of different ensembles for systems in equilibrium. We resolve this inconsistenc…
Deposition and evaporation of infinitely thin hard rods (needles) is studied in two dimensions using Monte Carlo simulations. The ratio of deposition to evaporation rates controls the equilibrium density of rods, and increasing it leads to an entropy-driven transition to a nematic phase in which both static and dynamical orientational correlation functions decay as power laws, with exponents varying continuously with deposition-evaporation rate ratio. Our results for the onset of the power-law phase agree with those for a conserved number of rods. At a coarse-grained level, the dynamics of the…
The interplay between electrostatic interactions and orientational correlations is studied for a model system of charged rods positioned on a chain, using Monte Carlo simulation techniques. It is shown that the coupling brings about the notion of {\em electrostatic frustration}, which in turn results in: (i) a rich variety of novel orientational orderings such as chiral phases, and (ii) an inherently slow dynamics characterized by stretched-exponential behavior in the relaxation functions of the system.
We study the dynamics of a one-dimensional fluid of orientable hard rectangles with a non-coarse-grained microscopic mechanism of facilitation. The length occupied by a rectangle depends on its orientation, which is coupled to an external field. The equilibrium properties of our model are essentially those of the Tonks gas, but at high densities, the orientational degrees of freedom become effectively frozen due to jamming. This is a simple analytically tractable model of glassy phase. Under a cyclic variation of the pressure, hysteresis is observed. Following a pressure quench, the orientatio…
This manuscript has been withdrawn because of significant overlap with an existing paper (Szabolcs Varga and Istvan Szalai, "Phase diagrams of binary mixtures of hard rods in an external orientational field", Phys. Chem. Chem. Phys., 2:1955-1959, 2000) of which we were, unfortunately, unaware when submitting our manuscript.
The equilibrium properties of hard rod monolayers are investigated in a lattice model (where position and orientation of a rod are restricted to discrete values) as well as in an off--lattice model featuring spherocylinders with continuous positional and orientational degrees of freedom. Both models are treated using density functional theory and Monte Carlo simulations. Upon increasing the density of rods in the monolayer, there is a continuous ordering of the rods along the monolayer normal ("standing up" transition). The continuous transition also persists in the case of an external potenti…
We study collections of self-propelled rods (SPR) moving in two dimensions for packing fractions less than or equal to 0.3. We find that in the thermodynamical limit the SPR undergo a phase transition between a disordered gas and a novel phase-separated system state. Interestingly, (global) orientational order patterns -- contrary to what has been suggested -- vanish in this limit. In the found novel state, the SPR self-organize into a highly dynamical, high-density, compact region - which we call aggregate - which is surrounded by a disordered gas. Active stresses build inside aggregates as r…
Spatially ordered systems confined to surfaces such as spheres exhibit interesting topological structures because of curvature induced frustration in orientational as well as translational order. The study of these structures is important for investigating the interplay between geometry, topology, and elasticity, and for their potential applications in materials science. In this work we numerically simulate a spherical monolayer of soft repulsive spherocylinders (SRS) and study the packing of rods and their ordering transition as a function of the packing fraction. In the model that we study, …
Roughness and orientational order in thin films of anisotropic particles are investigated using kinetic Monte Carlo simulations on a cubic lattice. Anisotropic next-neighbor interactions between the lattice particles were chosen to mimic the effects of shape anisotropy in the interactions of disc- or rod-like molecules with van-der-Waals attractions. Increasing anisotropy leads first to a preferred orientation in the film (which is close to the corresponding equilibrium transition) while the qualitative mode of roughness evolution (known from isotropic systems) does not change. At strong aniso…
The complete orientational ordering tensor of quasi-ideal colloidal rods is obtained as a function of shear rate by performing rheo-SANS (rheology with small angle neutron scattering) measurements on isotropic fd-virus suspensions in the two relevant scattering planes, the flow-gradient (1-2) and the flow-vorticity (1-3) plane. Microscopic ordering can be identified as the origin of the observed shear thinning. A qualitative description of the rheological response by Smoluchowski, as well as Doi--Edwards--Kuzuu theory is possible, as we obtain a master curve for different concentrations, scali…
We derive a model describing spatio-temporal organization of an array of microtubules interacting via molecular motors. Starting from a stochastic model of inelastic polar rods with a generic anisotropic interaction kernel we obtain a set of equations for the local rods concentration and orientation. At large enough mean density of rods and concentration of motors, the model describes an orientational instability. We demonstrate that the orientational instability leads to the formation of vortices and (for large density and/or kernel anisotropy) asters seen in recent experiments. We derive the…
We present a study of the isotropic-nematic interface in a system of hard spherocylinders. First we compare results from Monte Carlo simulations and Onsager density functional theory for the interfacial profiles of the orientational order parameter and the density. Those interfacial properties that are not affected by capillary waves are in good agreement, despite the fact that Onsager theory overestimates the coexistence densities. Then we show results of a Monte Carlo study of the capillary waves of the interface. In agreement with recent theoretical investigations (Eur.Phys.J. E {\bf 18} 40…
The phase behavior of a melt of monodisperse rod-coil diblocks is studied. We derive a Landau free energy functional for both a compositional and a nematic order parameter. The excluded volume interaction between the rod blocks is modeled by an attractive Maier-Saupe interaction. The incompatibility between rod- and coil blocks is modeled by the usual Flory-Huggins interaction. For a large volume fraction of the rods, a transition from isotropic to nematic to smectic C is observed upon decreasing the temperature, whereas for small rod volume fraction, spherical, hexagonal, and lamellar structu…
Self-assembly of particles with short-range attraction and long-range repulsion (SALR) interactions on a flat and on a spherical surface is compared. Molecular dynamics (MD) simulations are performed for the two systems having the same area and the density optimal for formation of stripes of particles. Structural characteristics, e.g. a cluster size distribution, a number of defects and an orientational order parameter (OP), as well as the specific heat, are obtained for a range of temperature. In both cases, the cluster size distribution becomes bimodal and elongated clusters appear at the te…
Using a combination of theory and experiments we study the interface between two immiscible domains in a colloidal membrane composed of rigid rods of different lengths. Geometric considerations of rigid rod packing imply that a domain of sufficiently short rods in a background membrane of long rods is more susceptible to twist than the inverse structure, a long-rod domain in a short-rod membrane background. The tilt at the inter-domain edge forces splay, which in turn manifests as a spontaneous edge curvature whose energetics are controlled by the length asymmetry of constituent rods. A thermo…
The orientational order in vertically agitated granular rod monolayers is investigated experimentally and compared quantitatively with equilibrium Monte Carlo simulations and density functional theory. At sufficiently high number density, short rods form a tetratic state and long rods form a uniaxial nematic state. The length-to-width ratio at which the order changes from tetratic to uniaxial is around $7.3$ in both experiments and simulations. This agreement illustrates the universal aspects of the ordering of rod-shaped particles across equilibrium and nonequilibrium systems. Moreover, the a…
The effect of strong confinement on the positional and orientational ordering is examined in a system of hard rectangular rods with length L and diameter D (L>D) using the Parsons-Lee modification of the second virial density functional theory. The rods are nonmesogenic (L/D<3)and confined between two parallel hard walls, where the width of the pore (H) is chosen in such a way that both planar (particle's long axis parallel to the walls) and homeotropic (particle's long axis perpendicular to the walls) orderings are possible and a maximum of two layers are allowed to form in the pore. In the e…
We study the orientational dynamics of heavy silica microrods flowing through a microfluidic channel. Comparing experiments and Brownian dynamics simulations we identify different particle orbits, in particular in-plane tumbling behavior, which cannot be explained by classical Jeffery theory, and we relate this behavior to the rotational diffusion of the rods. By constructing the full, three-dimensional, orientation distribution, we describe the rod trajectories and quantify the persistence of Jeffery orbits using temporal correlation functions of the Jeffery constant. We find that our colloid…
Using computer simulations, we explore how thermal noise-induced randomness in a self-assembled photonic crystal affects its photonic band gaps (PBGs). We consider a two-dimensional photonic crystal comprised of a self-assembled array of parallel dielectric hard rods of infinite length with circular or square cross section. We find the PBGs can exist over a large range of intermediate packing densities. Counterintuitively, the largest band gap does not always appear at the packing density where the crystal is most ordered, despite the randomness inherent in any self-assembled structure. For ro…
We study fluids of hard rods in the vicinity of hard spherical and cylindrical surfaces at densities below the isotropic-nematic transition. The Onsager second virial approximation is applied, which is known to yield exact results for the bulk properties in the limit of infinitely thin rods. This approach requires the computation of the one-particle distribution function and of the Mayer function which is greatly facilitated by an appropriate expansion in terms of spherical harmonics. We determine density and orientational profiles as well as the surface tension $γ$ as function of the surface …
Neicu and Kudrolli observed experimentally spontaneous formation of the long-range orientational order and large-scale vortices in a system of vibrated macroscopic rods. We propose a phenomenological theory of this phenomenon, based on a coupled system of equations for local rods density and tilt. The density evolution is described by modified Cahn-Hilliard equation, while the tilt is described by the Ginzburg-Landau type equation. Our analysis shows that, in accordance to the Cahn-Hilliard dynamics, the islands of the ordered phase appear spontaneously and grow due to coarsening. The generic …
We report on experiments to measure the temporal and spatial evolution of packing arrangements of anisotropic, cylindrical granular material, using high-resolution capacitive monitoring. In these experiments, the particle configurations start from an initially disordered, low-packing-fraction state and under vertical vibrations evolve to a dense, highly ordered, nematic state in which the long particle axes align with the vertical tube walls. We find that the orientational ordering process is reflected in a characteristic, steep rise in the local packing fraction. At any given height inside th…
We study the phase behaviour of the Zwanzig model of suspensions of hard rods, allowing for polydispersity in the lengths of the rods. In spite of the simplified nature of the model (rods are restricted to lie along one of three orthogonal axes), the results agree qualitatively with experimental observations: the coexistence region broadens significantly as the polydispersity increases, and strong fractionation occurs, with long rods found preferentially in the nematic phase. These conclusions are obtained from an analysis of the exact phase equilibrium equations. In the second part of the pap…
We study the orientational dynamics of infinitely thin hard rods of length L, with the centers-of-mass fixed on a simple cubic lattice with lattice constant a.We approximate the influence of the surrounding rods onto dynamics of a pair of rods by introducing an effective rotational diffusion constant D(l),l=L/a. We get D(l) ~ [1-v(l)], where v(l) is given through an integral of a time-dependent torque-torque correlator of an isolated pair of rods. A glass transition occurs at l_c, if v(l_c)=1. We present a variational and a numerically exact evaluation of v(l).Close to l_c the diffusion consta…
Using Monte Carlo simulation, we analyse the behaviour of two-dimensional hard rods in four different types of geometric confinement: (i) a slit pore where the particles are confined between two parallel walls with homeotropic anchoring; (ii) a hybrid slit pore formed by a planar and a homeotropic wall; square cavities that frustrate the orientational order by imposing either (iii) homeotropic or (iv) planar wall anchoring. We present results for the state diagram as a function of the packing fraction and the degree of confinement. Under extreme confinement, unexpected states appear with lower…
We investigate the ordering properties of vertically-vibrated monolayers of granular cylinders in a circular container at high packing fraction. In line with previous works by other groups, we identify liquid-crystalline ordering behaviour similar to that of two-dimensional hard rectangular particles subject to thermal equilibrium fluctuations. However, due to dissipation, there is a much stronger tendency for particles to cluster into parallel arrangements in the granular system. These clusters behave as a polydisperse mixture of long life-time `superparticles', and some aspects of the system…
It is known that when hard spheres are added to a pure system of hard rods the stability of the smectic phase may be greatly enhanced, and that this effect can be rationalised in terms of depletion forces. In the present paper we first study the effect of orientational order on depletion forces in this particular binary system, comparing our results with those obtained adopting the usual approximation of considering the rods parallel and their orientations frozen. We consider mixtures with rods of different aspect ratios and spheres of different diameters, and we treat them within Onsager theo…
Fluids consisting of hard platelike particles near a hard wall are investigated using density functional theory. The density and orientational profiles as well as the surface tension and the excess coverage are determined and compared with those of a fluid of rodlike particles. Even for low densities slight orientational packing effects are found for the platelet fluid due to larger intermolecular interactions between platelets as compared with those between rods. A net depletion of platelets near the wall is exhibited by the excess coverage, whereas a change of sign of the excess coverage of …
The implications of soft `patchy' interactions on the orientational disorder-order transition of strongly elongated colloidal rods and flat disks is studied within a simple Onsager-van der Waals density functional theory. The theory provides a generic framework for studying the liquid crystal phase behaviour of highly anisometric cylindrical colloids, which carry a distinct geometrical pattern of repulsive or attractive soft interactions localised on the particle surface. In this paper, we apply our theory to the case of charged rods and disks for which the local electrostatic interactions can…
Can a bath of isotropic but active particles promote ordering of anisotropic but passive particles? In this paper, we uncover a fluctuation-driven mechanism by which this is possible. Somewhat counter-intuitively, we show that the passive particles tend to be more ordered upon increasing the noise-strength of the active isotropic bath. We first demonstrate this in a general dynamical model for a non-conserved order parameter (model A) coupled to an active isotropic field and then concentrate on two examples, i. a collection of polar rods on a substrate in an active isotropic bath and ii. a pas…
The orientational dynamics of inertialess anisotropic particles transported by two-dimensional convective turbulent flows display a coexistence of regular and chaotic features. We numerically demonstrate that very elongated particles (rods) align preferentially with the direction of the fluid flow, i.e., horizontally close to the isothermal walls and dominantly vertically in the bulk. This behaviour is due to the the presence of a persistent large scale circulation flow structure, which induces strong shear at wall boundaries and in up/down-welling regions. The near-wall horizontal alignment o…
We study experimentally the nonequilibrium phase behaviour of a horizontal monolayer of macroscopic rods. The motion of the rods in two dimensions is driven by vibrations in the vertical direction. Aside from the control variables of packing fraction and aspect ratio that are typically explored in molecular liquid crystalline systems, due to the macroscopic size of the particles we are also able to investigate the effect of the precise shape of the particle on the steady states of this driven system. We find that the shape plays an important role in determining the nature of the orientational …
Using Monte Carlo simulation, we study a fluid of two-dimensional hard rods inside a small circular cavity bounded by a hard wall, from the dilute regime to the high-density, layering regime. Both planar and homeotropic anchoring of the nematic director can be induced at the walls through a free-energy penalty. The circular geometry creates frustration in the nematic phase and a polar-symmetry configuration with a distorted director field plus two $+1/2$ disclinations is created. At higher densities, a quasi-uniform structure is observed with a (minimal) director distortion which is relaxed vi…
Density functional theory is used to study colloidal hard-rod fluids near an individual right-angled wedge or edge as well as near a hard wall which is periodically patterned with rectangular barriers. The Zwanzig model, in which the orientations of the rods are restricted to three orthogonal orientations but their positions can vary continuously, is analyzed by numerical minimization of the grand potential. Density and orientational order profiles, excess adsorptions, as well as surface and line tensions are determined. The calculations exhibit an enrichment [depletion] of rods lying parallel…
We used the Density Functional formalism, in particular the Scaled Particle Theory, applied to a length-polydisperse hard-rectangular fluid to study its phase behavior as a function of the mean particle aspect ratio ($κ_0$) and polydispersity ($Δ_0$). The numerical solutions of the coexistence equations were calculated by transforming the original problem with infinite degrees of freedoms to a finite set of equations for the amplitudes of the Fourier expansion of the moments of the density profiles. We divided the study into two parts: The first one is devoted to the calculation of the phase d…
In the last 50 years, equilibrium density functional theory (DFT) has been proven to be a powerful, versatile and predictive approach for the statics and structure of classical particles. This theory can be extended to the nonequilibrium dynamics of completely overdamped Brownian colloidal particles towards so-called dynamical density functional theory (DDFT). The success of DDFT makes it a promising candidate for a first-principle description of active matter. In this lecture, we shall first recapitulate classical DDFT for passive colloidal particles typically described by Smoluchowski equati…
