Prediction of the liquid-crystal phase behavior of hard right triangles from fourth-virial density-functional theories.

We have used an extended scaled-particle theory that incorporates four-body correlations through the fourth-order virial coefficient to analyze the orientational properties of a fluid of hard right isosceles triangles. This fluid has been analyzed by computer simulation studies, with clear indications of strong octatic correlations present in the liquid-crystal phase, although the more symmetric order tetratic phase would seem to be the most plausible candidate. Standard theories based on the second virial coefficient are unable to reproduce this behavior. Our extended theory predicts that octatic correlations, associated to a symmetry under global rotations of the oriented fluid by 45^{∘}, are highly enhanced, but not enough to give rise to a thermodynamically stable phase with strict octatic symmetry. We discuss different scenarios to improve the theoretical understanding of the elusive octatic phase in this intriguing fluid.

Effect of combined roundness and polydispersity on the phase behavior of hard-rectangle fluids.

We introduce a model for a fluid of polydisperse rounded hard rectangles where the length and width of the rectangular core are fixed, while the roundness is taken into account by the convex envelope of a disk displaced along the perimeter of the core. The diameter of the disk has a continuous polydispersity described by a Schulz distribution function. We implemented the scaled particle theory for this model with the aim of studying: (i) the effect of roundness on the phase behavior of the one-component hard-rectangle fluid and (ii) how polydispersity affects phase transitions between isotropic, nematic, and tetratic phases. We found that roundness greatly affects the tetratic phase, whose region of stability in the phase diagram strongly decreases as the roundness parameter is increased. Also, the interval of aspect ratios where the tetratic-nematic and isotropic-nematic phase transitions are of first order considerably reduces with roundness, both transitions becoming weaker. Polydispersity induces strong fractionation between the coexisting phases, with the nematic phase enriched in particles of lower roundness. Finally, for high enough polydispersity and certain mean aspect ratios, the isotropic-to-nematic transition can change from second (for the one-component fluid) to first order. We also found a packing-fraction inversion phenomenon for large polydispersities: the coexisting isotropic phase has a higher packing fraction than the nematic.

Failure of standard density functional theory to describe the phase behavior of a fluid of hard right isosceles triangles.

A fluid of hard right isosceles triangles was studied using an extension of scaled-particle density-functional theory which includes the exact third virial coefficient. We show that the only orientationally ordered stable liquid-crystal phase predicted by the theory is the uniaxial nematic phase, in agreement with the second-order virial theory. By contrast, Monte Carlo simulations predict exotic liquid-crystal phases exhibiting tetratic and octatic correlations, with orientational distribution functions having four and eight equivalent peaks, respectively. This demonstrates the failure of the standard density-functional theory based on two- and three-body correlations to describe high-symmetry orientational phases in two-dimensional hard right-triangle fluids, and it points to the necessity to reformulate the theory to take into account high-order body correlations and ultimately particle self-assembling and clustering effects. This avenue may represent a great challenge for future research, and we discuss some fundamental ideas to construct a modified version of density-functional theory to account for these clustering effects.

Orientational ordering in a fluid of hard kites: A density-functional-theory study.

Using density-functional theory we theoretically study the orientational properties of uniform phases of hard kites-two isosceles triangles joined by their common base. Two approximations are used: scaled particle theory and a new approach that better approximates third virial coefficients of two-dimensional hard particles. By varying some of their geometrical parameters, kites can be transformed into squares, rhombuses, triangles, and also very elongated particles, even reaching the hard-needle limit. Thus, a fluid of hard kites, depending on the particle shape, can stabilize isotropic, nematic, tetratic, and triatic phases. Different phase diagrams are calculated, including those of rhombuses, and kites with two of their equal interior angles fixed to 90^{∘}, 60^{∘}, and 75^{∘}. Kites with one of their unequal angles fixed to 72^{∘}, which have been recently studied via Monte Carlo simulations, are also considered. We find that rhombuses and kites with two equal right angles and not too large anisometry stabilize the tetratic phase but the latter stabilize it to a much higher degree. By contrast, kites with two equal interior angles fixed to 60^{∘} stabilize the triatic phase to some extent, although it is very sensitive to changes in particle geometry. Kites with the two equal interior angles fixed to 75^{∘} have a phase diagram with both tetratic and triatic phases, but we show the nonexistence of a particle shape for which both phases are stable at different densities. Finally, the success of the new theory in the description of orientational order in kites is shown by comparing with Monte Carlo simulations for the case where one of the unequal angles is fixed to 72^{∘}. These particles also present a phase diagram with stable tetratic and triatic phases.

Highly confined mixtures of parallel hard squares: A density-functional-theory study.

Using the fundamental-measure density-functional theory, we study theoretically the phase behavior of extremely confined mixtures of parallel hard squares in slit geometry. The pore width is chosen such that configurations consisting of two consecutive big squares, or three small squares, in the transverse direction, perpendicular to the walls, are forbidden. We analyze two different mixtures with edge lengths of species selected so as to allow or forbid one big plus one small square to fit into the channel. For the first mixture we obtain first-order transitions between symmetric and asymmetric packings of particles: Small and big squares are preferentially adsorbed at different walls. Asymmetric configurations are shown to lead to more efficient packing at finite pressures. We argue that the stability region of the asymmetric phase in the pressure-composition plane is bounded so that the symmetric phase is stable at low and very high pressure. For the second mixture, we observe strong demixing between phases which are rich in different species. Demixing occurs in the lateral direction, i.e., the dividing interface is perpendicular to the walls, and phases exhibit symmetric density profiles. The possible experimental realization of this behavior (which in practical terms is precluded by jamming) in strictly two-dimensional systems is discussed. Finally, the phase behavior of a mixture with periodic boundary conditions is analyzed and the differences and similarities between the latter and the confined system are discussed. We claim that, although exact calculations exclude the existence of true phase transitions in (1+ε)-dimensional systems, density-functional theory is still successful in describing packing properties of large clusters of particles.

Uniform phases in fluids of hard isosceles triangles: One-component fluid and binary mixtures.

We formulate the scaled particle theory for a general mixture of hard isosceles triangles and calculate different phase diagrams for the one-component fluid and for certain binary mixtures. The fluid of hard triangles exhibits a complex phase behavior: (i) the presence of a triatic phase with sixfold symmetry, (ii) the isotropic-uniaxial nematic transition is of first order for certain ranges of aspect ratios, and (iii) the one-component system exhibits nematic-nematic transitions ending in critical points. We found the triatic phase to be stable not only for equilateral triangles but also for triangles of similar aspect ratios. We focus the study of binary mixtures on the case of symmetric mixtures: equal particle areas with aspect ratios (κ_{i}) symmetric with respect to the equilateral one, κ_{1}κ_{2}=3. For these mixtures we found, aside from first-order isotropic-nematic and nematic-nematic transitions (the latter ending in a critical point): (i) a region of triatic phase stability even for mixtures made of particles that do not form this phase at the one-component limit, and (ii) the presence of a Landau point at which two triatic-nematic first-order transitions and a nematic-nematic demixing transition coalesce. This phase behavior is analogous to that of a symmetric three-dimensional mixture of rods and plates.

Positional ordering of hard adsorbate particles in tubular nanopores.

The phase behavior and structural properties of a monolayer of hard particles is examined in such a confinement where the adsorbed particles are constrained to the surface of a narrow hard cylindrical pore. The diameter of the pore is chosen such that only first- and second-neighbor interactions occur between the hard particles. The transfer operator method of [Percus and Zhang, Mol. Phys. 69, 347 (1990)MOPHAM0026-897610.1080/00268979000100241] is reformulated to obtain information about the structure of the monolayer. We have found that a true phase transition is not possible in the examined range of pore diameters. The monolayer of hard spheres undergoes a structural change from fluidlike order to a zigzaglike solid one with increasing surface density. The case of hard cylinders is different in the sense that a layering takes place continuously between a low-density one-row and a high-density two-row monolayer. Our results reveal a clear discrepancy with classical density functional theories, which do not distinguish smecticlike ordering in bulk from that in narrow periodic pores.

Dynamical properties of heterogeneous nucleation of parallel hard squares.

We use the Dynamic Density-Functional Formalism and the Fundamental Measure Theory as applied to a fluid of parallel hard squares to study the dynamics of heterogeneous growth of non-uniform phases with columnar and crystalline symmetries. The hard squares are (i) confined between soft repulsive walls with a square symmetry, or (ii) exposed to external potentials that mimic the presence of obstacles with circular, square, rectangular or triangular symmetries. For the first case the final equilibrium profile of a well commensurated cavity consists of a crystal phase with highly localized particles in concentric square layers at the nodes of a slightly deformed square lattice. We characterize the growth dynamics of the crystal phase by quantifying the interlayer and intralayer fluxes and the non-monotonicity of the former, the saturation time, and other dynamical quantities. The interlayer fluxes are much more monotonic in time, and dominant for poorly commensurated cavities, while the opposite is true for well commensurated cells: although smaller, the time evolution of interlayer fluxes is much more complex, presenting strongly damped oscillations which dramatically increase the saturation time. We also study how the geometry of the obstacle affects the symmetry of the final equilibrium non-uniform phase (columnar vs. crystal). For obstacles with fourfold symmetry, (circular and square) the crystal is more stable, while the columnar phase is stabilized for obstacles without this symmetry (rectangular or triangular). We find that, in general, density waves of columnar symmetry grow from the obstacle. However, additional particle localization along the wavefronts gives rise to a crystalline structure which is conserved for circular and square obstacles, but destroyed for the other two obstacles where columnar symmetry is restored.

Role of length polydispersity in the phase behavior of freely rotating hard-rectangle fluids.

We use the density-functional formalism, in particular the scaled-particle theory, applied to a length-polydisperse hard-rectangle 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 are 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 divide the study into two parts. The first one is devoted to the calculation of the phase diagrams in the packing fraction η_{0}-κ_{0} plane for a fixed Δ_{0} and selecting parent distribution functions with exponential (the Schulz distribution) or Gaussian decays. In the second part we study the phase behavior in the η_{0}-Δ_{0} plane for fixed κ_{0} while Δ_{0} is changed. We characterize in detail the orientational ordering of particles and the fractionation of different species between the coexisting phases. Also we study the character (second vs first order) of the isotropic-nematic phase transition as a function of polydispersity. We particularly focus on the stability of the tetratic phase as a function of κ_{0} and Δ_{0}. The isotropic-nematic transition becomes strongly of first order when polydispersity is increased: The coexistence gap widens and the location of the tricritical point moves to higher values of κ_{0} while the tetratic phase is slightly destabilized with respect to the nematic one. The results obtained here can be tested in experiments on shaken monolayers of granular rods.

Ordering of hard rectangles in strong confinement.

Using transfer operator and fundamental measure theories, we examine the structural and thermodynamic properties of hard rectangles confined between two parallel hard walls. The side lengths of the rectangle (L and D, L>D) and the pore width (H) are chosen such that a maximum of two layers is allowed to form when the long sides of the rectangles are parallel to the wall, while only one layer is possible in case the rectangles are perpendicular to the wall. We observe three different structures: (i) at low density, the rectangles align mainly parallel to the wall, (ii) at intermediate or high density, two fluid layers form in which the rectangles are parallel to the wall, and (iii) a dense single fluid layer with rectangles aligned mainly perpendicular to the wall. The transition between these structures is smooth without any non-analytic behaviour in the thermodynamic quantities; however, the fraction of particles perpendicular (or parallel) to the wall can exhibit a relatively sudden change if L is close to H. In this case, interestingly, even three different structures can be observed with increasing density.

Biaxial nematic phase stability and demixing behaviour in monolayers of rod-plate mixtures.

We theoretically study the phase behaviour of monolayers of hard rod-plate mixtures using a fundamental-measure density functional in the restricted-orientation (Zwanzig) approximation. Particles can rotate in 3D but their centres of mass are constrained to be on a flat surface. In addition, we consider both species to be subject to an attractive potential proportional to the particle contact area on the surface and with adsorption strengths that depend on the species type. Particles have board-like shape, with sizes chosen using a symmetry criterion: same volume and same aspect ratio κ. Phase diagrams were calculated for κ = 10, 20 and 40 and different values of adsorption strengths. For small adsorption strengths the mixtures exhibit a second-order uniaxial nematic-biaxial nematic transition for molar fraction of rods 0 ≤x≲ 0.9. In the uniaxial nematic phase the particle axes of rods and plates are aligned perpendicular and parallel to the monolayer, respectively. At the transition, the orientational symmetry of the plate axes is broken, and they orient parallel to a director lying on the surface. For large and equal adsorption strengths the mixture demixes at low pressures into a uniaxial nematic phase, rich in plates, and a biaxial nematic phase, rich in rods. The demixing transition is located between two tricritical points. Also, at higher pressures and in the plate-rich part of the phase diagram, the system exhibits a strong first-order uniaxial nematic-biaxial nematic phase transition with a large density coexistence gap. When rod adsorption is considerably large while that of plates is small, the transition to the biaxial nematic phase is always of second order, and its region of stability in the phase diagram considerably widens. At very high pressures the mixture can effectively be identified as a two-dimensional mixture of squares and rectangles which again demixes above a certain critical point. We also studied the relative stability of uniform phases with respect to density modulations of smectic, columnar and crystalline symmetry.

Phase behaviour and correlations of parallel hard squares: from highly confined to bulk systems.

We study a fluid of two-dimensional parallel hard squares in bulk and under confinement in channels, with the aim of evaluating the performance of fundamental-measure theory (FMT). To this purpose, we first analyse the phase behaviour of the bulk system using FMT and Percus-Yevick (PY) theory, and compare the results with molecular dynamics and Monte Carlo simulations. In a second step, we study the confined system and check the results against those obtained from the transfer matrix method and from our own Monte Carlo simulations. Squares are confined to channels with parallel walls at angles of 0° or 45° relative to the diagonals of the parallel hard squares, respectively, which allows for an assessment of the effect of the external-potential symmetry on the fluid structural properties. In general FMT overestimates bulk correlations, predicting the existence of a columnar phase (absent in simulations) prior to crystallization. The equation of state predicted by FMT compares well with simulations, although the PY approach with the virial route is better in some range of packing fractions. The FMT is highly accurate for the structure and correlations of the confined fluid due to the dimensional crossover property fulfilled by the theory. Both density profiles and equations of state of the confined system are accurately predicted by the theory. The highly non-uniform pair correlations inside the channel are also very well described by FMT.

Effect of orientational restriction on monolayers of hard ellipsoids.

The effect of out-of-plane orientational freedom on the orientational ordering properties of a monolayer of hard ellipsoids is studied using the Parsons-Lee scaling approach and replica exchange Monte Carlo computer simulation. Prolate and oblate ellipsoids exhibit very different ordering properties, namely, the axes of revolution of prolate particles tend to lean out, while those of oblate ones prefer to lean into the confining plane. The driving mechanism of this is that the particles try to maximize the available free area on the confining surface, which can be achieved by minimizing the cross section areas of the particles with the plane. In the lack of out-of-plane orientational freedom the monolayer of prolate particles is identical to a two-dimensional hard ellipse system, which undergoes an isotropic-nematic ordering transition with increasing density. With gradually switching on the out-of-plane orientational freedom the prolate particles lean out from the confining plane and destabilisation of the in-plane isotropic-nematic phase transition is observed. The system of oblate particles behaves oppositely to that of prolates. It corresponds to a two-dimensional system of hard disks in the lack of out-of-plane freedom, while it behaves similar to that of hard ellipses in the freely rotating case. Solid phases can be realised by lower surface coverage due to the out-of-plane orientation freedom for both oblate and prolate shapes.

Capillary and winding transitions in a confined cholesteric liquid crystal.

We consider a Lebwohl-Lasher model of chiral particles confined in a planar cell (slit pore) under different boundary conditions, and solve it using mean-field theory. The phase behaviour of the system with respect to temperature and pore width is studied. Two phenomena are observed: (i) an isotropic-cholesteric transition, which exhibits an oscillatory structure with respect to pore width, and (ii) an infinite set of winding transitions caused by commensuration effects between cholesteric pitch and pore width. The latter transitions have been predicted and analysed by other authors for cholesterics confined in a fixed pore and subjected to an external field promoting the uniaxial nematic phase; here we induce winding transitions solely from geometry by changing the pore width at zero external field (a setup recently explored in atomic-force microscopy experiments). In contrast with previous studies, we obtain the phase diagram in the temperature vs. pore width plane, including the isotropic-cholesteric transition, the winding transitions and their complex relationship. In particular, the structure of winding transitions terminates at the capillary isotropic-cholesteric transition via triple points where the confined isotropic phase coexists with two cholesterics with different helix indices. For symmetric and asymmetric monostable plate anchorings the phase diagrams are qualitatively similar.

Effect of shape biaxiality on the phase behavior of colloidal liquid-crystal monolayers.

We extend our previous work on monolayers of uniaxial particles [J. Chem. Phys., 2014, 140, 204906] to study the effect of particle biaxiality on the phase behavior of liquid-crystal monolayers. Particles are modelled as board-like hard bodies with three different edge lengths σ1 ≥ σ2 ≥ σ3, and the restricted-orientation approximation (Zwanzig model) is used. A density-functional formalism based on the fundamental-measure theory is used to calculate phase diagrams for a wide range of values with the largest aspect ratio κ1 = σ1/σ3 ∈ [1,100]. We find that particle biaxiality in general destabilizes the biaxial nematic phase already present in monolayers of uniaxial particles. While plate-like particles exhibit strong biaxial ordering, rod-like ones with κ1 > 21.34 exhibit reentrant uniaxial and biaxial phases. As particle geometry is changed from uniaxial- to increasingly biaxial-rod-like, the region of biaxiality is reduced, eventually ending in a critical-end point. For κ1 > 60, a density gap opens up in which the biaxial nematic phase is stable for any particle biaxiality. Regions of the phase diagram, where packing-fraction inversion occurs (i.e. packing fraction is a decreasing function of density), are found. Our results are compared with the recent experimental studies on nematic phases of magnetic nanorods.

Hard-body models of bulk liquid crystals.

Hard models for particle interactions have played a crucial role in the understanding of the structure of condensed matter. In particular, they help to explain the formation of oriented phases in liquids made of anisotropic molecules or colloidal particles and continue to be of great interest in the formulation of theories for liquids in bulk, near interfaces and in biophysical environments. Hard models of anisotropic particles give rise to complex phase diagrams, including uniaxial and biaxial nematic phases, discotic phases and spatially ordered phases such as smectic, columnar or crystal. Also, their mixtures exhibit additional interesting behaviours where demixing competes with orientational order. Here we review the different models of hard particles used in the theory of bulk anisotropic liquids, leaving aside interfacial properties and discuss the associated theoretical approaches and computer simulations, focusing on applications in equilibrium situations. The latter include one-component bulk fluids, mixtures and polydisperse fluids, both in two and three dimensions, and emphasis is put on liquid-crystal phase transitions and complex phase behaviour in general.

Phase behaviour of liquid-crystal monolayers of rod-like and plate-like particles.

Orientational and positional ordering properties of liquid crystal monolayers are examined by means of Fundamental-Measure Density Functional Theory. Particles forming the monolayer are modeled as hard parallelepipeds of square section of size σ and length L. Their shapes are controlled by the aspect ratio κ = L/σ (>1 for prolate and <1 for oblate shapes). The particle centers of mass are restricted to a flat surface and three possible and mutually perpendicular orientations (in-plane and along the layer normal) of their uniaxial axes are allowed. We find that the structure of the monolayer depends strongly on particle shape and density. In the case of rod-like shapes, particles align along the layer normal in order to achieve the lowest possible occupied area per particle. This phase is a uniaxial nematic even at very low densities. In contrast, for plate-like particles, the lowest occupied area can be achieved by random in-plane ordering in the monolayer, i.e., planar nematic ordering takes place even at vanishing densities. It is found that the random in-plane ordering is not favorable at higher densities and the system undergoes an in-plane ordering transition forming a biaxial nematic phase or crystallizes. For certain values of the aspect ratio, the uniaxial-biaxial nematic phase transition is observed for both rod-like and plate-like shapes. The stability region of the biaxial nematic phase enhances with decreasing aspect ratios for plate-like particles, while the rod-like particles exhibit a reentrant phenomenon, i.e., a sequence of uniaxial-biaxial-uniaxial nematic ordering with increasing density if the aspect ratio is larger than 21.34. In addition to this, packing fraction inversion is observed with increasing surface pressure due to the alignment along the layers normal. At very high densities the nematic phase destabilizes to a nonuniform phases (columnar, smectic, or crystalline phases) for both shapes.

Hard rods in a cylindrical pore: the nematic-to-smectic phase transition.

The effect of cylindrical confinement on the phase behaviour of a system of parallel hard rods is studied using Onsager's second-virial theory. The hard rods are represented as hard cylinders of diameter D and length L, while the cylindrical pore is infinite with diameter W. The interaction between the wall and the rods is hard repulsive, and it is assumed that molecules are parallel to the surface of the pore (planar anchoring). In very narrow pores (D < W < 2D), the structure is homogeneous and the system behaves as a one-dimensional Tonks gas. For wider pores, inhomogeneous fluid structures emerge because of the lowering of the average excluded volume due to the wall-particle interaction. The bulk nematic-smectic A phase transition is replaced by a transition between inhomogeneous nematic and smectic A phases. The smectic is destabilized with respect to the nematic for decreasing pore width; this effect becomes substantial for W < 10D. For W > 100D, results for bulk and confined fluids agree well due to the short range effect of the wall (∼ 3-4D).

Interplay between columnar and smectic stability in suspensions of polydisperse colloidal platelets.

The phase behavior of a model suspension of colloidal polydisperse platelets is studied using density-functional theory. Platelets are modelled as parallel rectangular prisms of square section l(2) and height h, with length and height distributions given by different polydispersities δ(l) and δ(h). The model is intended to qualitatively represent experimental colloidal platelet suspensions at high densities with a high degree of orientational ordering. We obtain the phase behavior of the model, including nematic, smectic and columnar phases and its dependence on the two polydispersities δ(l) and δ(h). When δ(l) > δ(h) we observe that the smectic phase stabilises first with respect to the columnar. If δ(h) > δ(l) we observe the opposite behavior. Other more complicated cases occur, e.g. the smectic stabilises from the nematic first but then exists a first-order transition to the columnar phase. Our model assumes plate-rod symmetry, but the regions of stability of smectic and columnar phases are non-symmetric in the δ(l) - δ(h) plane due to the different dimensionality of ordering in the two phases. Microsegregation effects, i.e. different spatial distribution for different sizes within the periodic cell, take place in both phases and, in each case, is more apparent in the variable associated with ordering.

Liquid-crystal patterns of rectangular particles in a square nanocavity.

Using density-functional theory in the restricted-orientation approximation, we analyze the liquid-crystal patterns and phase behavior of a fluid of hard rectangular particles confined in a two-dimensional square nanocavity of side length H composed of hard inner walls. Patterning in the cavity is governed by surface-induced order as well as capillary and frustration effects and depends on the relative values of the particle aspect ratio κ≡L/σ, with L the length and σ the width of the rectangles (L≥σ), and cavity size H. Ordering may be very different from bulk (H→∞) behavior when H is a few times the particle length L (nanocavity). Bulk and confinement properties are obtained for the cases κ=1, 3, and 6. In bulk the isotropic phase is always stable at low packing fractions η=Lσρ_{0} (with ρ_{0} the average density) and nematic, smectic, columnar, and crystal phases can be stabilized at higher η depending on κ: For increasing η the sequence of isotropic to columnar is obtained for κ=1 and 3, whereas for κ=6 we obtain isotropic to nematic to smectic (the crystal being unstable in all three cases for the density range explored). In the confined fluid surface-induced frustration leads to fourfold symmetry breaking in all phases (which become twofold symmetric). Since no director distortion can arise in our model by construction, frustration in the director orientation is relaxed by the creation of domain walls (where the director changes by 90^{∘}); this configuration is necessary to stabilize periodic phases. For κ=1 the crystal becomes stable with commensurate transitions taking place as H is varied. These transitions involve structures with different number of peaks in the local density. In the case κ=3 the commensurate transitions involve columnar phases with different number of columns. In the case κ=6 the high-density region of the phase diagram is dominated by commensurate transitions between smectic structures; at lower densities there is a symmetry-breaking isotropic to nematic transition exhibiting nonmonotonic behavior with cavity size. Apart from the present application in a confinement setup, our model could be used to explore the bulk region near close packing in order to elucidate the possible existence of disordered phases at close packing.