Hard-disk Mixtures Research Articles

Inverse design of crystals and quasicrystals in a non-additive binary mixture of hard disks.

The development of new materials typically involves a process of trial and error, guided by insights from past experimental and theoretical findings. The inverse design approach for soft-matter systems has the potential to optimize specific physical parameters, such as particle interactions, particle shape, or composition and packing fraction. This optimization aims to facilitate the spontaneous formation of specific target structures through self-assembly. In this study, we expand upon a recently introduced inverse design protocol for monodisperse systems to identify the required conditions and interactions for assembling crystal and quasicrystal phases within a binary mixture of two distinct species. This method utilizes an evolution algorithm to identify the optimal state point and interaction parameters, enabling the self-assembly of the desired structure. In addition, we employ a convolutional neural network (CNN) that classifies different phases based on their diffraction patterns, serving as a fitness function for the desired structure. Using our protocol, we successfully inverse design two-dimensional crystalline structures, including a hexagonal lattice and a dodecagonal quasicrystal, within a non-additive binary mixture of hard disks. Finally, we introduce a symmetry-based order parameter that leverages the encoded symmetry within the diffraction pattern. This order parameter circumvents the need for training a CNN and is used as a fitness function to inverse design an octagonal quasicrystal.

Dynamic neighbours: a proposal of a tool to characterize phase transitions

For molecular dynamics simulations of hard particles, we define dynamic neighbours as the distinct particles that collide with a given reference one during a specific time interval. This definition allows us to determine the distribution of the number of dynamic neighbours, its average, and its standard deviation. We will show that regardless of the time window used to identify dynamic neighbours, their distribution is correlated with diffusion coefficients, structure, and configurational entropy. Thus, it is likely that the distribution of the number of dynamic neighbours may be employed as another tool to gain insights into the dynamic behaviour of hard-core systems. We tested this approach on 2D and 3D systems consisting of monodisperse and binary mixtures of hard disks and spheres. Results show that implementing dynamic neighbours to define order parameters can sharpen the signals where transitions take place.

Two-dimensional ordering of bacteriorhodopsins in a lipid bilayer and effects caused by repulsive core between lipid molecules on lateral depletion interaction: A study based on a thermodynamic perturbation theory

Using binary hard disk mixture models, we studied the two-dimensional ordering of bacteriorhodopsins in a lipid bilayer. The phase diagrams were calculated using the thermodynamic perturbation theory. We examined two types of effective interactions to discuss the lateral depletion effects caused by repulsive core interaction between lipid molecules. The results indicate that the core repulsions drastically broaden the coexistence region for the fluid-ordered phase.

Two-Dimensional Melting of Two- and Three-Component Mixtures.

We elucidate the interplay between diverse two-dimensional melting pathways and establish solid-hexatic and hexatic-liquid transition criteria via the numerical simulations of the melting transition of two- and three-component mixtures of hard polygons and disks. We show that a mixture's melting pathway may differ from its components and demonstrate eutectic mixtures that crystallize at a higher density than their pure components. Comparing the melting scenario of many two- and three-component mixtures, we establish universal melting criteria: the solid and hexatic phases become unstable as the density of topological defects, respectively, overcomes ρ_{d,s}≃0.046 and ρ_{d,h}≃0.123.

Density of binary disc packings: Playing with stoichiometry

We consider hard-disc mixtures with disc sizes within ratio 2−1, that is, the small disc exactly fits in the hole between four large discs. For each prescribed stoichiometry of large and small discs, the densest packings are rigorously determined via a computer-assisted proof. The density is maximal for the 1:1 stoichiometry: the large discs then form a square grid in each interstitial site of which a small disc nests. When there is an excess of large discs, the densest packings are made of a single phase which mixes the two types of discs in a chaotic way (it can be described by square-triangle tilings). When there is an excess of small discs, on the contrary, a phenomenon of phase separation appears: the large discs are involved in the densest 1:1 stoichiometry phases while the excess of small discs form compact hexagonal phases.

Theory and equation of state of two-component nonadditive hard-disks: an application in the colloidal regime

ABSTRACT We use theoretical and Monte Carlo computer simulations to study thermodynamic and structural properties of a binary mixture of nonadditive hard-disks. The nonadditivity parameter is set to assume negative values so as to favour heterocoordination between the two species. The theoretical approaches include the Rescaled Virial Expansion Equation of State, which is based on the knowledge of the virial coefficients of the mixture, and the Rogers-Young Integral-Equation Theory. The comparison with Monte Carlo data shows that the microscopic theory is able to provide a reliable prediction of both the equation of state and the radial distribution functions of the system. These results are of interest because binary mixtures of colloidal particles adsorbed at the interface exhibit a wide range of self-assembly phenomena, and achieving of a reliable fluid state theory for a simple model of these systems is an essential milestone to be able to understand their nature.

Bridging hexatic and tetratic phases in binary mixtures through near critical point fluctuations

Monte Carlo simulations were used to study the assembly of model binary mixtures whose pure components have either distinct or similar crystal order symmetry. Specifically, we simulated mixtures of hard disks with either squares or hexagons, where the components have size ratios that optimize their co-assembly into compositionally disordered solids. For the disks + squares mixture, along with the enhanced regions of solid miscibility, we report a continuous-looking transition from the disklike to the squarelike behavior that occurs through a region that seamlessly bridges the regions of hexatic phase of disks and the tetratic phase of squares, which we term the mosaic ($M$) region. For the equimolar composition, this $M$ region is bound by the isotropic phase at low pressures and by the hexatic-tetratic (two-phase) macrophase segregated region above a critical transition pressure. Our analysis showed that the $M$ region lies in the vicinity of the critical point, manifesting local compositional fluctuations that give rise to microphase segregated regions of interspersed square-rich fourfold and rhombic lattice symmetry and disk-rich sixfold clusters that coexist across the system. The $M$ behavior is characterized by a short-ranged translational order and an algebraic decay of the correlation functions for sixfold and fourfold orientational order. A finite size scaling analysis was used to evaluate the dependence of the local compositional susceptibility with system size to extract the critical exponent associated with the approach of the critical point. For the disks + hexagons mixture, a fully mixed hexatic phase was observed for all compositions.

Minimal statistical-mechanical model for multihyperuniform patterns in avian retina

Birds are known for their extremely acute sense of vision. The very peculiar structural distribution of five different types of cones in the retina underlies this exquisite ability to sample light. It was recently found that each cone population as well as their total population display a disordered pattern in which long-wavelength density fluctuations vanish [Jiao etal., Phys. Rev. E 89, 022721 (2014)PLEEE81539-375510.1103/PhysRevE.89.022721]. This property, known as hyperuniformity, is also present in perfect crystals. In situations like the avian retina in which both the global structure and that of each component display hyperuniformity, the system is said to be multihyperuniform. In this work, we aim at devising a minimal statistical-mechanical model that can reproduce the main features of the spatial distribution of photoreceptors in avian retina, namely the presence of disorder, multihyperuniformity, and local heterocoordination. This last feature is key to avoiding local clustering of the same type of photoreceptors, an undesirable feature for the efficient sampling of light. For this purpose, we formulate a minimal statistical-mechanical model that definitively exhibits the required structural properties: an equimolar three-component mixture (one component to sample each primary color: red, green, and blue) of nonadditive hard disks to which a long-range logarithmic repulsion is added between like particles. Interestingly, a Voronoi analysis of our idealized system of photoreceptors shows that the space-filling Voronoi polygons display a rather uniform area distribution, symmetrically centered around that of a regular lattice, a structural property also found in human retina. Disordered multihyperuniformity offers an alternative to generate photoreceptor patterns with minimal long-range concentration and density fluctuations. This is the key to overcoming the difficulties in devising an efficient visual system in which crystal-like order is absent.

Infinite-pressure phase diagram of binary mixtures of (non)additive hard disks.

One versatile route to the creation of two-dimensional crystal structures on the nanometer to micrometer scale is the self-assembly of colloidal particles at an interface. Here, we explore the crystal phases that can be expected from the self-assembly of mixtures of spherical particles of two different sizes, which we map to (additive or non-additive) hard-disk mixtures. We map out the infinite-pressure phase diagram for these mixtures using Floppy Box Monte Carlo simulations to systematically sample candidate crystal structures with up to 12 disks in the unit cell. As a function of the size ratio and the number ratio of the two species of particles, we find a rich variety of periodic crystal structures. Additionally, we identify random tiling regions to predict random tiling quasicrystal stability ranges. Increasing non-additivity both gives rise to additional crystal phases and broadens the stability regime for crystal structures involving a large number of large-small contacts, including random tilings. Our results provide useful guidelines for controlling the self-assembly of colloidal particles at interfaces.

Equation of State of Four- and Five-Dimensional Hard-Hypersphere Mixtures

New proposals for the equation of state of four- and five-dimensional hard-hypersphere mixtures in terms of the equation of state of the corresponding monocomponent hard-hypersphere fluid are introduced. Such proposals (which are constructed in such a way so as to yield the exact third virial coefficient) extend, on the one hand, recent similar formulations for hard-disk and (three-dimensional) hard-sphere mixtures and, on the other hand, two of our previous proposals also linking the mixture equation of state and the one of the monocomponent fluid but unable to reproduce the exact third virial coefficient. The old and new proposals are tested by comparison with published molecular dynamics and Monte Carlo simulation results and their relative merit is evaluated.

Scaling with a fractional power: Overcoming the shortage of scaled-particle variables for the hard-disk fluid.

Within scaled-particle theory, we construct an equation of state (EOS) for hard-disk mixtures by making use of an additional scaled-particle variable which weighs the densities of the different components by its radii to the power χ. This allows us to simultaneously respect exact results pertaining to the cases of a large particle or a point particle being added to the mixture. In the limit χ → 2, the mixture EOS of Santos et al. [Mol. Phys. 96, 1 (1999)] is recovered, while the limit χ → 0 yields the accurate expression for the interfacial free energy of Martin et al. [J. Chem. Phys. 149, 084701 (2018)]. From the low-density limit of the EOS, the value χ ≈ 0.8 is extracted, which is shown to yield a mixture EOS that is significantly more accurate than the expressions due to Santos et al. and Martin et al. In particular, the systematic deviation inherent to these prior results is remedied.

Thermodynamics of the hard-disk fluid at a planar hard wall: Generalized scaled-particle theory and Monte Carlo simulation.

A generalized scaled-particle theory for the uniform hard-disk mixture is derived in the spirit of the White Bear II free energy of the hard-sphere fluid [H. Hansen-Goos and R. Roth, J. Phys. C: Condens. Matter 18, 8413 (2006)]. The theory provides a very simple result for the interfacial free energy γ of the hard-disk fluid at a planar hard wall (which in d = 2 is a line) in terms of the equation of state. To complement and assess the theory, we perform Monte Carlo simulations from which we obtain γ using Gibbs-Cahn integration. While we find excellent overall agreement between theory and simulation, it also becomes apparent that the set of scaled-particle variables available in d = 2 is too limited, prohibiting a quasi-exact result for γ. Furthermore, this is reflected in the mixture equation of state resulting from our theory, which, similar to a previous attempt by Santos et al. [Mol. Phys. 96, 1 (1999)], displays a small but systematic deviation from simulations.

Effective osmotic cohesion due to the solvent molecules in a delocalized adsorbed monolayer

A molecular thermodynamic model is derived for an uncharged delocalized surfactant monolayer adsorbed at a liquid interface, taking explicit account for the solvent molecules present in the monolayer. The model is based on the scaled particle theory of hard-disc mixtures, and is also extended to sticky discs (i.e. attraction between the adsorbed molecules). Upon compression of the adsorbed layer, the solvent is expelled from it. The respective osmotic effect on the equation of state is shown to be equivalent to an effective lateral depletion attraction between the surfactant molecules. This effective osmotic cohesion causes an increase of the value of the attraction parameter β of the monolayer. The smaller the size of the surfactant polar head group is, the larger the effective attraction the model predicts. This trend is verified with data for the adsorption at water|air surface of alcohols, undissociated acids, and hexaethylenglycol monoalkyl ethers. The proposed theory allows the amount of solvent in the monolayer to be estimated, which is shown to be important for the neutron reflectivity of the surface.

Phase diagrams and crystal-fluid surface tensions in additive and nonadditive two-dimensional binary hard-disk mixtures.

Using density functionals from fundamental measure theory, phase diagrams and crystal-fluid surface tensions in additive and nonadditive (Asakura-Oosawa model) two-dimensional binary hard-disk mixtures are determined for the whole range of size ratios q=smalldiameter/largediameter, assuming random disorder (lattice points or interstitial occupied by large or small disks at random) in the crystal phase. The fluid-crystal transitions are first order due to the assumption of a periodic unit cell in the density-functional calculations. Qualitatively, the shape of the phase diagrams is similar to the case of three-dimensional hard-sphere mixtures. For the nonadditive case, a broadening of the fluid-crystal coexistence region is found for small q, whereas for large q a vapor-fluid transition intervenes. In the additive case, we find a sequence of spindle-type, azeotropic, and eutectic phase diagrams upon lowering q from 1 to 0.6. The transition from azeotropic to eutectic is different from the three-dimensional case. Surface tensions in general become smaller (up to a factor 2) upon addition of a second species and they are rather small. The minimization of the functionals proceeds without restrictions and optimized graphics card routines are used.

Communication: Contact values of pair distribution functions in colloidal hard disks by test-particle insertion.

We apply Henderson's method for measuring the cavity distribution function y(r) [J. Henderson, Mol. Phys. 48, 389 (1983)] to obtain the pair distribution function at contact, g(σ+). In contrast to the conventional distance-histogram method, no approximate extrapolation to contact is required. The resulting equation of state from experiments and simulations of hard disks agrees well with the scaled particle theory prediction up to high fluid packing fractions. We also provide the first experimental measurement of y(r) inside the hard core, which will allow for a more complete comparison with theory. The method's flexibility is further illustrated by measuring the partial pair distribution functions of binary hard-disk mixtures in simulation. The equation for the contact values can be used to derive familiar results from statistical geometry.

Elastic moduli of a Brownian colloidal glass former

The static, dynamic and flow-dependent shear moduli of a binary mixture of Brownian hard disks are studied by an event-driven molecular dynamics simulation. Thereby, the emergence of rigidity close to the glass transition encoded in the static shear modulus is accessed by three methods. Results from shear stress auto-correlation functions, elastic dispersion relations, and the elastic response to strain deformations upon the start-up of shear flow are compared. This enables one to sample the time-dependent shear modulus consistently over several decades in time. By that a very precise specification of the glass transition point and of is feasible. Predictions by mode coupling theory of a finite shear modulus at the glass transition, of α-scaling in fluid states close to the transition, and of shear induced decay in yielding glass states are tested and broadly verified.

Equation of state of polydisperse hard-disk mixtures in the high-density regime.

A proposal to link the equation of state of a monocomponent hard-disk fluid to the equation of state of a polydisperse hard-disk mixture is presented. Event-driven molecular dynamics simulations are performed to obtain data for the compressibility factor of the monocomponent fluid and of 26 polydisperse mixtures with different size distributions. Those data are used to assess the proposal and to infer the values of the compressibility factor of the monocomponent hard-disk fluid in the metastable region from those of mixtures in the high-density region. The collapse of the curves for the different mixtures is excellent in the stable region. In the metastable regime, except for two mixtures in which crystallization is present, the outcome of the approach exhibits a rather good performance. The simulation results indicate that a (reduced) variance of the size distribution larger than about 0.01 is sufficient to avoid crystallization and explore the metastable fluid branch.

Virial coefficients, equation of state, and demixing of binary asymmetric nonadditive hard-disk mixtures

Values of the fifth virial coefficient, compressibility factors, and fluid-fluid coexistence curves of binary asymmetric nonadditive mixtures of hard disks are reported. The former correspond to a wide range of size ratios and positive nonadditivities and have been obtained through a standard Monte Carlo method for the computation of the corresponding cluster integrals. The compressibility factors as functions of density, derived from canonical Monte Carlo simulations, have been obtained for two values of the size ratio (q = 0.4 and q = 0.5), a value of the nonadditivity parameter (Δ = 0.3), and five values of the mole fraction of the species with the biggest diameter (x1 = 0.1, 0.3, 0.5, 0.7, and 0.9). Some points of the coexistence line relative to the fluid-fluid phase transition for the same values of the size ratios and nonadditivity parameter have been obtained from Gibbs ensemble Monte Carlo simulations. A comparison is made between the numerical results and those that follow from some theoretical equations of state.

Disappearance of the Hexatic Phase in a Binary Mixture of Hard Disks.

Recent studies of melting in hard disks have confirmed the existence of a hexatic phase occurring in a narrow window of density which is separated from the isotropic liquid phase by a first-order transition, and from the solid phase by a continuous transition. However, little is known concerning the melting scenario in mixtures of hard disks. Here we employ tailored MonteCarlo simulations to elucidate the phase behavior of a system of large (l) and small (s) disks with diameter ratio σ_{l}/σ_{s}=1.4. We find that as small disks are introduced to a system of large ones, the stability window of the hexatic phase shrinks progressively until the line of continuous transitions terminates at an end point beyond which melting becomes a first-order liquid-solid transition. This occurs at surprisingly low concentrations of the small disks, c≲1%, emphasizing the fragility of the hexatic phase. We speculate that the change to the melting scenario is a consequence of strong fractionation effects, the nature of which we elucidate.

Transport coefficients and mechanical response in hard-disk colloidal suspensions**Project supported by the National Basic Research Program of China (Grant No. 2012CB821500) and the National Natural Science Foundation of China (Grant Nos. 21374073 and, 21574096).

We investigate the transport properties and mechanical response of glassy hard disks using nonlinear Langevin equation theory. We derive expressions for the elastic shear modulus and viscosity in two dimensions on the basis of thermal-activated barrier-hopping dynamics and mechanically accelerated motion. Dense hard disks exhibit phenomena such as softening elasticity, shear-thinning of viscosity, and yielding upon deformation, which are qualitatively similar to dense hard-sphere colloidal suspensions in three dimensions. These phenomena can be ascribed to stress-induced “landscape tilting”. Quantitative comparisons of these phenomena between hard disks and hard spheres are presented. Interestingly, we find that the density dependence of yield stress in hard disks is much more significant than in hard spheres. Our work provides a foundation for further generalizing the nonlinear Langevin equation theory to address slow dynamics and rheological behavior in binary or polydisperse mixtures of hard or soft disks.