Materials undergoing both phase separation and chemical reactions (defined here as all processes that change particle type or number) form an important class of non-equilibrium systems. Examples range from suspensions of self-propelled bacteria with birth-death dynamics, to bio-molecular condensates, or 'membraneless organelles', within cells. In contrast to their passive counterparts, such systems have conserved and non-conserved dynamics that do not, in general, derive from a shared free energy. This mismatch breaks time-reversal symmetry and leads to new types of dynamical competition that are absent in or near equilibrium. We construct a canonical scalar field theory to describe such systems, with conserved and non-conserved dynamics obeying Model B and Model A respectively (in the Hohenberg-Halperin classification), chosen such that the two free energies involved are incompatible. The resulting minimal model is shown to capture the various phenomenologies reported previously for more complicated models with the same physical ingredients, including microphase separation, limit cycles and droplet splitting. We find a low-dimensional subspace of parameters for which time-reversal symmetry is accidentally recovered, and show that here the dynamics of the order parameter field (but not its conserved current) is exactly the same as an equilibrium system in which microphase separation is caused by long-range attractive interactions.
We describe a Monte Carlo scheme for the grand canonical simulation study of fluid phase equilibria in highly size-asymmetrical binary mixtures. The method utilizes an expanded ensemble in which the insertion and deletion of large particles is accomplished {\em gradually} by traversing a series of states in which a large particle interacts only partially with the environment of small particles. Free energy barriers arising from interfacial coexistence states are surmounted with the aid of multicanonical preweighting, the associated weights being determined from the transition matrix. As an ill…
We perform a linearization of the Poisson-Boltzmann (PB) density functional for spherical Wigner-Seitz cells that yields Debye-Hückel-like equations agreeing asymptotically with the PB results in the weak-coupling (high-temperature) limit. Both the canonical (fixed number of microions) as well as the semi-grand-canonical (in contact with an infinite salt reservoir) cases are considered and discussed in a unified linearized framework. In the canonical case, for sufficiently large colloidal charges the linearized theory predicts the occurrence of a thermodynamical instability with an associated …
In patchy particle systems where there is competition between the self-assembly of finite clusters and liquid-vapour phase separation, reentrant phase behaviour is observed, with the system passing from a monomeric vapour phase to a region of liquid-vapour phase coexistence and then to a vapour phase of clusters as the temperature is decreased at constant density. Here, we present a classical statistical mechanical approach to the determination of the complete phase diagram of such a system. We model the system as a van der Waals fluid, but one where the monomers can assemble into monodisperse…
We study the phase behavior and the interfacial tension of the screened Coulomb (Yukawa) restricted primitive model (YRPM) of oppositely charged hard spheres with diameter s using Monte Carlo simulations. We determine the gas-liquid and gas-solid phase transition using free energy calculations and grand-canonical Monte Carlo simulations for varying inverse Debye screening length k. We find that the gas-liquid phase separation is stable for k s <= 4, and that the critical temperature decreases upon increasing the screening of the interaction (decreasing the range of the interaction). In additio…
We study theoretically the equilibrium phase behaviour of a mixture of polydisperse hard-sphere colloids and monodisperse polymers, modelled using the Asakura-Oosawa model within the free volume approximation of Lekkerkerker et al. We compute full phase diagrams in the plane of colloid and polymer volume fractions, using the moment free energy method. The intricate features of phase separation in pure polydisperse colloids combine with the appearance of polymer-induced gas-liquid coexistence to give a rich variety of phase diagram topologies as the polymer-colloid size ratio and the colloid po…
We study the phase ordering colloids suspended in a thermotropic nematic liquid crystal below the clearing point Tni and the resulting aggregated structure. Small (150nm) PMMA particles are dispersed in a classical liquid crystal matrix, 5CB or MBBA. With the help of confocal microscopy we show that small colloid particles densely aggregate on thin interfaces surrounding large volumes of clean nematic liquid, thus forming an open cellular structure, with the characteristic size of 10-100 micron inversely proportional to the colloid concentration. A simple theoretical model, based on the Landau…
We report the behaviour of mixtures of fine bronze and glass spheres under sinusoidal vertical vibration. Depending upon the ratio of their diameters and the amplitude and frequency of the vibration, we observe the formation of sharp separation boundaries between glass-rich and bronze-rich phases, the absence of gross convection which would mix these phases, and a number of oscillatory and non-periodic behaviours. These phenomena are related to the differential air damping of the glass and bronze grains, disappearing completely in the absence of air.
We develop a general theory for describing phase coexistence between nonequilibrium steady states in Brownian systems, based on power functional theory (M. Schmidt and J.M. Brader, J. Chem. Phys. 138, 214101 (2013)). We apply the framework to the special case of fluid-fluid phase separation of active soft sphere swimmers. The central object of the theory, the dissipated free power, is calculated via computer simulations and compared to a simple analytical approximation. The theory describes well the simulation data and predicts motility-induced phase separation due to avoidance of dissipative …
The effect of polydispersity on the phase behaviour of hard spheres is examined using a moment projection method. It is found that the Boublik-Mansoori-Carnahan-Starling-Leland equation of state shows a spinodal instability for a bimodal distribution if the large spheres are sufficiently polydisperse, and if there is sufficient disparity in mean size between the small and large spheres. The spinodal instability direction points to the appearance of a very dense phase of large spheres.
Recently, there has been much interest in activity-induced phase separations in concentrated suspensions of "active Brownian particles" (ABPs), self-propelled spherical particles whose direction of motion relaxes through thermal rotational diffusion. To date, almost all these studies have been restricted to 2 dimensions. In this work we study activity-induced phase separation in 3D and compare the results with previous and new 2D simulations. To this end, we performed state-of-the-art Brownian dynamics simulations of up to 40 million ABPs -- such very large system sizes are unavoidable to evad…
Simulation studies of the phase diagram of repulsive active Brownian particles in three dimensions reveal that the region of motility-induced phase separation between a high and low density phase is enclosed by a region of gas-crystal phase separation. Near-critical loci and structural crossovers can additionally be identified in analogy with simple fluids. Motivated by the striking similarity to the behaviour of equilibrium fluids with short-ranged pair-wise attractions, we show that a direct mapping to pair potentials in the dilute limit implies interactions that are insufficiently attractiv…
A grand canonical Monte Carlo method for the simulation of a simple colloid-polymer mixture called the AO model will be described. The phase separation known to occur in this model is driven by entropy. The phase diagram of the unmixing transition, the surface tension and thecritical point will be determined. To appear in: "Computer Simulation Studies in Condensed Matter Physics XVIII, Eds. D.P. Landau, S.P. Lewis, and H.B. Schuettler (Springer Verlag, Heidelberg, Berlin, 2004).
A two-component system of penetrable particles interacting via a gaussian core potential is considered, which may serve as a crude model for binary polymer solutions. The pair structure and thermodynamic properties are calculated within the random phase approximation (RPA) and the hypernetted chain (HNC) integral equation. The analytical RPA predictions are in semi-quantitative agreement with the numerical solutions of the HNC approximation, which itself is very accurate for gaussian core systems. A fluid-fluid phase separation is predicted to occur for a broad range of potential parameters. T…
We investigate the phase behaviour of random copolymers melts via large scale Monte Carlo simulations. We observe macrophase separation into A and B--rich phases as predicted by mean field theory only for systems with a very large correlation lambda of blocks along the polymer chains, far away from the Lifshitz point. For smaller values of lambda, we find that a locally segregated, disordered microemulsion--like structure gradually forms as the temperature decreases. As we increase the number of blocks in the polymers, the region of macrophase separation further shrinks. The results of our Mon…
DNA has the potential to realize a controllable liquid-liquid phase separation (LLPS) system, because the design of its base sequences results in programmable interactions. Here, we have developed a novel DNA-based LLPS system which enables us to create 'DNA droplets' and to control their dynamic behaviour by designing sequences of the DNA nanostructure. We were able to change the phase separation temperature required for the formation of DNA droplets by designing the sequences. In addition, the fusion, fission, and formation of Janus-shaped droplets were controlled by sequence design and enzy…
Mechanical interactions between biological cells may be mediated by secreted products, making them dependent on the local particle density. Here, we explore the generic physics of density-dependent attractive interactions. We show using Brownian dynamics simulations that density-dependent interactions can produce interesting phase separation behaviour including control of aggregate size during a spinodal decomposition-like separation process. We show that these results are generic using continuum modelling of the appropriate Cahn-Hilliard equation. Our study suggests that density-dependent int…
We derive a mean-field free energy for the phase behaviour of coupled bilayer leaflets, which is implicated in cellular processes and important to the design of artificial membranes. Our model accounts for amphiphile-level structural features, particularly hydrophobic mismatch, which promotes antiregistration (AR), in competition with the `direct' trans-midplane coupling usually studied, promoting registration (R). We show that the phase diagram of coupled leaflets allows multiple \textit{metastable} coexistences, then illustrate the kinetic implications with a detailed study of a bilayer of e…
We have recently investigated the phase behaviour of model colloidal dumbbells constituted by two identical tangent hard spheres, with the first one being surrounded by an attractive square-well interaction (Janus dumbbells, Munaò G et al 2014 Soft Matter 10 5269). Here we extend our previous analysis by introducing in the model the size asymmetry of the hard-core diameters, and study the enriched phase scenario thereby obtained. By employing standard Monte Carlo simulations we show that in such "heteronuclear Janus dumbbells" a larger hard-sphere site promotes the formation of clusters, where…
We simulate clustering, phase separation and hexatic ordering in a monolayered suspension of active squirming disks subject to an attractive Lennard-Jones-like pairwise interaction potential, taking hydrodynamic interactions between the particles fully into account. By comparing the hydrodynamic case with counterpart simulations for passive and active Brownian particles, we elucidate the relative roles of self-propulsion, interparticle attraction, and hydrodynamic interactions in determining clustering and phase behaviour. Even in the presence of an attractive potential, we find that hydrodyna…
We report canonical and grand-canonical lattice Monte Carlo simulations of the self-assembly of addressable structures comprising hundreds of distinct component types. The nucleation behaviour, in the form of free-energy barriers to nucleation, changes significantly as the co-ordination number of the building blocks is changed from 4 to 8 to 12. Unlike tetrahedral structures - which roughly correspond to DNA bricks that have been studied in experiment - the shapes of the free-energy barriers of higher co-ordination structures depend strongly on the supersaturation, and such structures require …
We investigate the behaviour of randomly cross-linked (co)polymer blends using a combination of replica theory and large-scale molecular dynamics simulations. In particular, we derive the analogue of the random phase approximation for systems with quenched disorder and show how the required correlation functions can be calculated efficiently. By post-processing simulation data for homopolymer networks we are able to describe neutron scattering measurements in heterogeneous systems without resorting to microscopic detail and otherwise unphysical assumptions. We obtain structure function data wh…
Behaviour of the model antibody fluid constrained by rigid spherical obstacles: effects of the obstacle-antibody binding
University of Ljubljana, Faculty of Chemistry and Chemical Technology（卢布尔雅那大学化学与化学技术学院）；Yukhnovskii Institute for Condensed Matter Physics of the National Academy of Sciences of Ukraine（乌克兰国家科学院尤赫诺夫斯基凝聚态物理研究所）；Institute of Applied Mathematics and Fundamental Sciences, Lviv Polytechnic National University（利沃夫国立理工大学应用数学与基础科学研究所）
Colloidal particles that are confined to an interface such as the air-water interface are an example of a two-dimensional fluid. Such dispersions have been observed to spontaneously form cluster and stripe morphologies in certain systems with isotropic pair potentials between the particles, due to the fact that the pair interaction between the colloids has competing attraction and repulsion over different length scales. Here we present a simple density functional theory for a model of such a two-dimensional fluid. The theory predicts a bulk phase diagram exhibiting cluster, stripe and bubble m…
The Leibler theory [L. Leibler, Macromolecules, v.13, 1602 (1980)] for microphase separation in AB block copolymer melts is generalized for systems with arbitrary topology of molecules. A diagrammatic technique for calculation of the monomeric correlation functions is developed. The free energies of various mesophases are calculated within the second-harmonic approximation. Model highly-branched tree-like structures are considered as an example and their phase diagrams are obtained. The topology of molecules is found to influence the spinodal temperature and asymmetry of the phase diagrams, bu…
We study the equilibrium behaviour of a mixture of monodisperse hard sphere colloids and polydisperse non-adsorbing polymers at their $θ$-point, using the Asakura-Oosawa model treated within the free-volume approximation. Our focus is the experimentally relevant scenario where the distribution of polymer chain lengths across the system is fixed. Phase diagrams are calculated using the moment free energy method, and we show that the mean polymer size $ξ_{\rm c}$ at which gas-liquid phase separation first occurs decreases with increasing polymer polydispersity $δ$. Correspondingly, at fixed mean…
