Friction on incommensurate substrates: Role of anharmonicity and defects.

We present molecular dynamics simulations of one- and two-dimensional bead-spring models sliding on incommensurate substrates after an initial kick, in the case where the coupling to the underlying substrate is weak, i.e., energy can dissipate only into the internal degrees of freedom of the sliding object, but not into the substrate below. We investigate how sliding friction is affected by structural defects and interaction anharmonicity. In their absence, we confirm earlier findings, namely, that at special resonance sliding velocities, friction is maximal. When sliding off-resonance, partially thermalized states are possible, whereby only a small number of vibrational modes becomes excited, but whose kinetic energies are already Maxwell-Boltzmann distributed. Anharmonicity and defects typically destroy partial thermalization and instead lead to full thermalization, implying much higher friction. For sliders with periodic boundaries, thermalization begins with vibrational modes whose spatial modulation is compatible with the incommensurate lattice. For a disk-shaped slider, modes corresponding to modulations compatible with the slider radius are initially the most dominant. By tuning the mechanical properties of the slider's edge, this effect can be controlled, resulting in significant changes in the sliding distance covered.

Main transition in the Pink membrane model: finite-size scaling and the influence of surface roughness.

We consider the main transition in single-component membranes using computer simulations of the Pink model [D. A. Pink et al., Biochemistry 19, 349 (1980)]. We first show that the accepted parameters of the Pink model yield a main transition temperature that is systematically below experimental values. This resolves an issue that was first pointed out by Corvera and co-workers [Phys. Rev. E 47, 696 (1993)]. In order to yield the correct transition temperature, the strength of the van der Waals coupling in the Pink model must be increased; by using finite-size scaling, a set of optimal values is proposed. We also provide finite-size scaling evidence that the Pink model belongs to the universality class of the two-dimensional Ising model. This finding holds irrespective of the number of conformational states. Finally, we address the main transition in the presence of quenched disorder, which may arise in situations where the membrane is deposited on a rough support. In this case, we observe a stable multidomain structure of gel and fluid domains, and the absence of a sharp transition in the thermodynamic limit.

Phase separation in fluids exposed to spatially periodic external fields.

When a fluid is confined within a spatially periodic external field, the liquid-vapor transition is replaced by a different transition called laser-induced condensation (LIC) [Götze et al., Mol. Phys. 101, 1651 (2003)]. In d=3 dimensions, the periodic field induces an additional phase, characterized by large density modulations along the field direction. At the triple point, all three phases (modulated, vapor, and liquid) coexist. At temperatures slightly above the triple point and for low (high) values of the chemical potential, two-phase coexistence between the modulated phase and the vapor (liquid) is observed; by increasing the temperature further, both coexistence regions terminate in critical points. In this paper, we reconsider LIC using the Ising model to resolve a number of open issues. To be specific, we (1) determine the universality class of the LIC critical points and elucidate the nature of the correlations along the field direction, (2) present a mean-field analysis to show how the LIC phase diagram changes as a function of the field wavelength and amplitude, (3) develop a simulation method by which the extremely low tension of the interface between modulated and vapor or liquid phase can be measured, (4) present a finite-size scaling analysis to accurately extract the LIC triple point from finite-size simulation data, and (5) consider the fate of LIC in d=2 dimensions.

Fluids with quenched disorder: scaling of the free energy barrier near critical points.

In the context of Monte Carlo simulations, the analysis of the probability distribution P(L)(m) of the order parameter m, as obtained in simulation boxes of finite linear extension L, allows for an easy estimation of the location of the critical point and the critical exponents. For Ising-like systems without quenched disorder, P(L)(m) becomes scale-invariant at the critical point, where it assumes a characteristic bimodal shape featuring two overlapping peaks. In particular, the ratio between the value of P(L)(m) at the peaks (P(L, max)) and the value at the minimum in between (P(L, min)) becomes L-independent at criticality. However, for Ising-like systems with quenched random fields, we argue that instead ΔF(L) := ln(P(L, max)/P(L, min)) proportional to L(θ) should be observed, where θ > 0 is the 'violation of hyperscaling' exponent. Since θ is substantially non-zero, the scaling of ΔF(L) with system size should be easily detectable in simulations. For two fluid models with quenched disorder, ΔF(L) versus L was measured and the expected scaling was confirmed. This provides further evidence that fluids with quenched disorder belong to the universality class of the random field Ising model.

Domain formation in membranes with quenched protein obstacles: lateral heterogeneity and the connection to universality classes.

We show that lateral fluidity in membranes containing quenched protein obstacles belongs to the universality class of the two-dimensional random-field Ising model. The main feature of this class is the absence of a phase transition: there is no critical point and macroscopic domain formation does not occur. Instead there is only one phase. This phase is highly heterogeneous with a structure consisting of microdomains. The presence of quenched protein obstacles thus provides a mechanism to stabilize lipid rafts in equilibrium. Crucial for two-dimensional random-field Ising universality is that the obstacles are randomly distributed and have a preferred affinity to one of the lipid species. When these conditions are not met standard Ising or diluted Ising universality applies. In these cases a critical point does exist which then marks the onset toward macroscopic demixing.

Isotropic-to-nematic transition in confined liquid crystals: an essentially nonuniversal phenomenon.

Computer simulations are presented of the isotropic-to-nematic transition in a liquid crystal confined between two parallel plates a distance H apart. The plates are neutral and do not impose any anchoring on the particles. Depending on the shape of the pair potential acting between the particles, we find that the transition either changes from first order to continuous at a critical film thickness H=H(x) , or that the transition remains first order irrespective of H . This demonstrates that the isotropic-to-nematic transition in confined geometry is not characterized by any universality class, but rather that its fate is determined by microscopic details. The resulting capillary phase diagrams can thus assume two topologies: one where the isotropic and nematic branches of the binodal meet at H=H(x), and one where they remain separated. For values of H where the transition is strongly first order the shift Deltaepsilon of the transition temperature is in excellent agreement with the Kelvin equation. Not only is the relation Deltaepsilon proportional, variant 1/H recovered but also the prefactor of the shift is in quantitative agreement with the independently measured bulk latent heat and interfacial tension.

Finite-size scaling in Ising-like systems with quenched random fields: evidence of hyperscaling violation.

In systems belonging to the universality class of the random field Ising model, the standard hyperscaling relation between critical exponents does not hold, but is replaced with a modified hyperscaling relation. As a result, standard formulations of finite-size scaling near critical points break down. In this work, the consequences of modified hyperscaling are analyzed in detail. The most striking outcome is that the free-energy cost ΔF of interface formation at the critical point is no longer a universal constant, but instead increases as a power law with system size, ΔF∝L(θ), with θ as the violation of hyperscaling critical exponent and L as the linear extension of the system. This modified behavior facilitates a number of numerical approaches that can be used to locate critical points in random field systems from finite-size simulation data. We test and confirm the approaches on two random field systems in three dimensions, namely, the random field Ising model and the demixing transition in the Widom-Rowlinson fluid with quenched obstacles.

Nematics with quenched disorder: violation of self-averaging.

We consider the isotropic-to-nematic transition in liquid crystals confined to aerogel hosts, and assume that the aerogel acts as a random field. We generally find that self-averaging is violated. For a bulk transition that is weakly first order, the violation of self-averaging is so severe that even the correlation length becomes non-self-averaging: no phase transition remains in this case. For a bulk transition that is more strongly first order, the violation of self-averaging is milder, and a phase transition is observed.

The Widom-Rowlinson mixture on a sphere: elimination of exponential slowing down at first-order phase transitions.

Computer simulations of first-order phase transitions using 'standard' toroidal boundary conditions are generally hampered by exponential slowing down. This is partly due to interface formation, and partly due to shape transitions. The latter occur when droplets become large such that they self-interact through the periodic boundaries. On a spherical simulation topology, however, shape transitions are absent. We expect that by using an appropriate bias function, exponential slowing down can be largely eliminated. In this work, these ideas are applied to the two-dimensional Widom-Rowlinson mixture confined to the surface of a sphere. Indeed, on the sphere, we find that the number of Monte Carlo steps needed to sample a first-order phase transition does not increase exponentially with system size, but rather as a power law τ α V(α), with α≈2.5, and V the system area. This is remarkably close to a random walk for which α(RW) = 2. The benefit of this improved scaling behavior for biased sampling methods, such as the Wang-Landau algorithm, is investigated in detail.

Liquid crystals in two dimensions: first-order phase transitions and nonuniversal critical behavior.

Liquid crystals in two dimensions undergo a first-order isotropic-to-quasi-nematic transition, provided the particle interactions are sufficiently "sharp and narrow." This implies phase coexistence between isotropic and quasi-nematic domains, separated by interfaces. The corresponding line tension is determined and shown to be very small, giving rise to strong interface fluctuations. When the interactions are no longer "sharp and narrow," the transition becomes continuous, with nonuniversal critical behavior obeying hyperscaling and approximately resembling the two-dimensional Potts model.

Phase diagram and structure of colloid-polymer mixtures confined between walls.

The influence of confinement, due to flat parallel structureless walls, on phase separation in colloid-polymer mixtures, is investigated by means of grand-canonical Monte Carlo simulations. Ultrathin films, with thicknesses between D=3-10 colloid diameters, are studied. The Asakura-Oosawa model [J. Chem. Phys. 22, 1255 (1954)] is used to describe the particle interactions. To simulate efficiently, a "cluster move" [J. Chem. Phys. 121, 3253 (2004)] is used in conjunction with successive umbrella sampling [J. Chem. Phys. 120, 10925 (2004)]. These techniques, when combined with finite size scaling, enable an accurate determination of the unmixing binodal. Our results show that the critical behavior of the confined mixture is described by "effective" critical exponents, which gradually develop from values near those of the two-dimensional Ising model, to those of the three-dimensional Ising model, as D increases. The scaling predictions of and Fisher and Nakanishi [J. Chem. Phys. 75, 5875 (1981)] for the shift of the critical point are compatible with our simulation results. Surprisingly, however, the colloid packing fraction at criticality approaches its bulk (D-->infinity) value nonmonotonically, as D is increased. Far from the critical point, our results are compatible with the simple Kelvin equation, implying a shift of order 1/D in the coexistence colloid chemical potential. We also present density profiles and pair distribution functions for a number of state points on the binodal, and the influence of the colloid-wall interaction is studied.

Critical behavior in colloid-polymer mixtures: theory and simulation.

We extensively investigated the critical behavior of mixtures of colloids and polymers via the two-component Asakura-Oosawa model and its reduction to a one-component colloidal fluid using accurate theoretical and simulation techniques. In particular the theoretical approach, hierarchical reference theory [A. Parola and L. Reatto, Adv. Phys. 44, 211 (1995)], incorporates realistically the effects of long-range fluctuations on phase separation giving exponents which differ strongly from their mean-field values, and are in good agreement with those of the three-dimensional Ising model. Computer simulations combined with finite-size scaling analysis confirm the Ising universality and the accuracy of the theory, although some discrepancy in the location of the critical point between one-component and full-mixture description remains. To assess the limit of the pair-interaction description, we compare one-component and two-component results.

Coexistence diameter in two-dimensional colloid-polymer mixtures.

We demonstrate that the law of the rectilinear coexistence diameter in two-dimensional mixtures of nonspherical colloids and nonadsorbing polymers is violated. Upon approach to the critical point, the diameter shows logarithmic singular behavior governed by a term t ln t, with t the relative distance from the critical point. No sign of a term t2beta could be detected, with beta the critical exponent of the order parameter, indicating a very weak or absent Yang-Yang anomaly. Our analysis thus reveals that nonspherical particle shape alone is not sufficient for the formation of a pronounced Yang-Yang anomaly in the critical behavior of fluids.

Critical behavior of a colloid-polymer mixture confined between walls.

We investigate the influence of confinement on phase separation in colloid-polymer mixtures. To describe the particle interactions, the colloid-polymer model of Asakura and Oosawa [J. Chem. Phys. 22, 1255 (1954)] is used. Grand canonical Monte Carlo simulations are then applied to this model confined between two parallel hard walls, separated by a distance D = 5 colloid diameters. We focus on the critical regime of the phase separation and look for signs of crossover from three-dimensional (3D) Ising to two-dimensional (2D) Ising universality. To extract the critical behavior, finite size scaling techniques are used, including the recently proposed algorithm of Kim et al [Phys. Rev. Lett. 91, 065701 (2003)]. Our results point to "effective" critical exponents that differ profoundly from 3D Ising values, and that are already very close to 2D Ising values. In particular, we observe that the critical exponent of the order parameter in the confined system is smaller than in 3D bulk, yielding a "flatter" binodal. Our results also show an increase in the critical colloid packing fraction in the confined system with respect to the bulk. The latter seems consistent with theoretical expectations, although subtleties due to singularities in the critical behavior of the coexistence diameter cannot be ruled out.

Critical behavior of the Widom-Rowlinson mixture: coexistence diameter and order parameter.

The critical behavior of the Widom-Rowlinson [J. Chem. Phys. 52, 1670 (1970)] is studied in d = 3 dimensions by means of grand canonical Monte Carlo simulations. The finite-size scaling approach of Kim et al. [Phys. Rev. Lett. 91, 065701 (2003)] is used to extract the order parameter and the coexistence diameter. It is demonstrated that the critical behavior of the diameter is dominated by a singular term proportional to t(1-alpha), with t the relative distance from the critical point, and alpha the critical exponent of the specific heat. No sign of a term proportional to t(2beta) could be detected, with beta the critical exponent of the order parameter, indicating that pressure mixing in this model is small. The critical density is measured to be rhosigma3 = 0.7486 +/- 0.0002, with sigma the particle diameter. The critical exponents alpha and beta, as well as the correlation length exponent nu, are also measured and shown to comply with d = 3 Ising criticality.

Critical behavior of colloid-polymer mixtures in random porous media.

We show that the critical behavior of a colloid-polymer mixture inside a random porous matrix of quenched hard spheres belongs to the universality class of the random-field Ising model. We also demonstrate that random-field effects in colloid-polymer mixtures are surprisingly strong. This makes these systems attractive candidates to study random-field behavior experimentally.

Bulk and interfacial properties in colloid-polymer mixtures.

Large-scale Monte Carlo simulations of a phase-separating colloid-polymer mixture are performed and compared to recent experiments. The approach is based on effective interaction potentials in which the central monomers of self-avoiding polymer chains are used as effective coordinates. By incorporating polymer nonideality together with soft colloid-polymer repulsion, the predicted binodal is in excellent agreement with recent experiments. In addition, the interfacial tension as well as the capillary length are in quantitative agreement with experimental results obtained at a number of points in the phase-coexistence region, without the use of any fit parameters.

Isotropic-nematic interfacial tension of hard and soft rods: application of advanced grand canonical biased-sampling techniques.

Coexistence between the isotropic and the nematic phase in suspensions of rods is studied using grand canonical Monte Carlo simulations with a bias on the nematic order parameter. The biasing scheme makes it possible to estimate the interfacial tension gamma(IN) in systems of hard and soft rods. For hard rods with LD=15, we obtain gammaIN approximately 1.4kBT/L2, with L the rod length, D the rod diameter, T the temperature, and kB the Boltzmann constant. This estimate is in good agreement with theoretical predictions, and the order of magnitude is consistent with experiments.

Simulation and theory of fluid demixing and interfacial tension of mixtures of colloids and nonideal polymers.

An extension of the Asakura-Oosawa-Vrij model of hard sphere colloids and nonadsorbing polymers is studied with grand canonical Monte Carlo simulations and density functional theory. Polymer nonideality is taken into account through a repulsive step-function pair potential between polymers. Simulation results validate previous theoretical findings for the shift of the bulk fluid demixing binodal upon increasing strength of polymer-polymer repulsion, indicating suppression of phase separation. For increasing strength of the polymer-polymer repulsion, simulation and theory consistently predict the interfacial tension of the free interface between the colloidal liquid and the colloidal gas phase to decrease significantly for fixed colloid density difference in the coexisting phases, and to increase for fixed polymer reservoir packing fraction.

Interfacial tension of the isotropic-nematic interface in suspensions of soft spherocylinders.

The isotropic to nematic transition in a system of soft spherocylinders is studied by means of grand canonical Monte Carlo simulations. The probability distribution of the particle density is used to determine the coexistence densities of the isotropic and the nematic phases. The distributions are also used to compute the interfacial tension of the isotropic-nematic interface, including an analysis of finite size effects. Our results confirm that the Onsager limit is not recovered until for very large elongation, exceeding at least L/D=40 , with L the spherocylinder length and D the diameter. For smaller elongation, we find that the interfacial tension increases with increasing L/D , in agreement with theoretical predictions.