Binary Hard-sphere Mixtures Research Articles

Rigidity of a spherical capsule switches the localization of encapsulated particles between inner and peripheral regions under crowding condition: Simple model on cellular architecture

We have investigated the inhomogeneous interior of confined spherical cavities as capsules containing encapsulated binary hard sphere mixtures for different compositions and cavity wall rigidity. Such a greatly simplified model manifests the effects of macromolecular crowding arising from excluded volume interactions in a tiny cell or a cellular nucleus. By fixing the number of large particles, the level of crowding is adjusted by changing the amount of small hard spheres in the cavity. For a rigid cavity, large spheres tend to pack in liquid-like order apart from the surface to the center of the cavity as the crowding level is increased. Whereas, for a soft cavity, larger spheres tend to blend with small spheres in the peripheral region at near the boundary of the cavity, and are susceptible to be depleted from the interior of the cavity as the cavity becomes more crowded. These results may help future elucidation of the thermodynamic pathways to stabilize the inhomogeneous structure of mixtures confined in cavities, such as the derepression of genome materials around the interior rim of the nucleus in a cancerous cell.

Calculation of the interfacial free energy of a binary hard-sphere fluid at a planar hard wall

Using molecular-dynamics simulation and Gibbs-Cahn Integration, we calculate the interfacial free energy γ of a binary hard-sphere fluid mixture at a structureless, planar hard wall. The calculation is performed as a function of packing fraction (density) for several values of the diameter ratio α = σ2∕σ1, where σ1 and σ2 are the diameters of the two particle types in the mixture. Our results are compared to those obtained from the bulk version of the White Bear Mark II (WBII) classical density-functional theory, which is a modification of the Fundamental-Measure Theory of Rosenfeld. The WBII bulk theory is shown to be in very good agreement with the simulation results, with significant deviation only at the very highest packing fractions.

Note: Depletion potentials in non-additive asymmetric binary mixtures of hard-spheres

First Page

Crucial Importance of Protein-Solvent Many-Body Correlation for Solvent-Entropy Effect in Structural Stability of a Protein

Using a hybrid method of the integral equation theory and the morphometric approach, we have shown that the solvent-entropy effect originating from the protein-solvent many-body correlation plays essential roles in the protein-folding mechanism [1], sugar-induced enhancement of the thermal stability [2], and pressure [3] and cold [4] denaturating of a protein. Here we revisit the roles of the many-body correlation in a variety of folding/unfolding processes to investigate the effects of solvent models on the contributions from the pair and many-body correlations to the solvent-entropy change upon a protein structural transition. We employ the two models of one-component solvent: a multipolar model for water and a hard-sphere solvent where the number density and the molecular diameter are set at those of water. In the model water the contribution from the many-body correlation is substantially larger than that from the pair one, whereas in the hard-sphere solvent the many-body correlation makes only a much smaller contribution. This result suggests that solvent-solvent interactions such as hydrogen bonds have large effects on the relative contributions from the two correlations. In the hard-sphere solvent, the native structure remains the most stable even at low temperatures and the swelling (i.e., pressure-denatured) structure is more stable than the native structure even at normal pressure. However, in the binary mixture of hard spheres with high packing fractions, which we have employed for investigating the sugar-induced enhancement, the many-body correlation makes a suitably large contribution.[1] T. Yoshidome et al., J. Chem. Phys. 128, 225104 (2008).[2] H. Oshima and M. Kinoshita, J. Chem. Phys. 138, 245101 (2013).[3] Y. Harano et al., J. Chem. Phys. 129, 145103 (2008).[4] H. Oshima et al., J. Chem. Phys. 131, 205102 (2009).

Demixing and nematic behaviour of oblate hard spherocylinders and hard spheres mixtures: Monte Carlo simulation and Parsons–Lee theory

Parsons–Lee approach is formulated for the isotropic–nematic transition in a binary mixture of oblate hard spherocylinders and hard spheres. Results for the phase coexistence and for the equation of state in both phases for fluids with different relative size and composition ranges are presented. The predicted behaviour is in agreement with Monte Carlo simulations in a qualitative fashion. The study serves to provide a rational view of how to control key aspects of the behaviour of these binary nematogenic colloidal systems. This behaviour can be tuned with an appropriate choice of the relative size and molar fractions of the depleting particles. In general, the mixture of discotic and spherical particles is stable against demixing up to very high packing fractions. We explore in detail the narrow geometrical range where demixing is predicted to be possible in the isotropic phase. The influence of molecular crowding effects on the stability of the mixture when spherical molecules are added to a system of discotic colloids is also studied.

Demixing transition, structure, and depletion forces in binary mixtures of hard-spheres: The role of bridge functions

Asymmetric binary mixtures of hard-spheres exhibit several interesting thermodynamic phenomena, such as multiple kinds of glassy states. When the degrees of freedom of the small spheres are integrated out from the description, their effects are incorporated into an effective pair interaction between large spheres known as the depletion potential. The latter has been widely used to study both the phase behavior and dynamic arrest of the big particles. Depletion forces can be accounted for by a contraction of the description in the multicomponent Ornstein-Zernike equation [R. Castañeda-Priego, A. Rodríguez-López, and J. M. Méndez-Alcaraz, Phys. Rev. E 73, 051404 (2006)]. Within this theoretical scheme, an approximation for the difference between the effective and bare bridge functions is needed. In the limit of infinite dilution, this difference is irrelevant and the typical Asakura-Osawa depletion potential is recovered. At higher particle concentrations, however, this difference becomes important, especially where the shell of first neighbors is formed, and, as shown here, cannot be simply neglected. In this work, we use a variant of the Verlet expression for the bridge functions to highlight their importance in the calculation of the depletion potential at high densities and close to the spinodal decomposition. We demonstrate that the modified Verlet closure predicts demixing in binary mixtures of hard spheres for different size ratios and compare its predictions with both liquid state and density functional theories, computer simulations, and experiments. We also show that it provides accurate correlation functions even near the thermodynamic instability; this is explicitly corroborated with results of molecular dynamics simulations of the whole mixture. Particularly, our findings point toward a possible universal behavior of the depletion potential around the spinodal line.

Effects of sugars on the thermal stability of a protein

It is experimentally known that the heat-denaturation temperature of a protein is raised (i.e., its thermal stability is enhanced) by sugar addition. In earlier works, we proposed a physical picture of thermal denaturation of proteins in which the measure of the thermal stability is defined as the solvent-entropy gain upon protein folding at 298 K normalized by the number of residues. A multipolar-model water was adopted as the solvent. The polyatomic structures of the folded and unfolded states of a protein were taken into account in the atomic detail. A larger value of the measure implies higher thermal stability. First, we show that the measure remains effective even when the model water is replaced by the hard-sphere solvent whose number density and molecular diameter are set at those of real water. The physical picture is then adapted to the elucidation of the effects of sugar addition on the thermal stability of a protein. The water-sugar solution is modeled as a binary mixture of hard spheres. The thermal stability is determined by a complex interplay of the diameter of sugar molecules dC and the total packing fraction of the solution η: dC is estimated from the volume per molecule in the sugar crystal and η is calculated using the experimental data of the solution density. We find that the protein is more stabilized as the sucrose or glucose concentration becomes higher and the stabilization effect is stronger for sucrose than for glucose. These results are in accord with the experimental observations. Using a radial-symmetric integral equation theory and the morphometric approach, we decompose the change in the measure upon sugar addition into two components originating from the protein-solvent pair and protein-solvent many-body correlations, respectively. Each component is further decomposed into the excluded-volume and solvent-accessible-surface terms. These decompositions give physical insights into the microscopic origin of the thermal-stability enhancement by sugar addition. As an example, the higher stability of the native state relative to that of the unfolded state is found to be attributable primarily to an increase in the solvent crowding caused by sugar addition. Due to the hydrophilicity of sugar molecules, the addition of sugar by a larger amount or that with a larger molecular size leads to an increase in η which is large enough to make the solvent crowding more serious.

Free energy barriers for homogeneous crystal nucleation in a eutectic system of binary hard spheres

In this study, the free energy barriers for homogeneous crystal nucleation in a system that exhibits a eutectic point are computed using Monte Carlo simulations. The system studied is a binary hard sphere mixture with a diameter ratio of 0.85 between the smaller and larger hard spheres. The simulations of crystal nucleation are performed for the entire range of fluid compositions. The free energy barrier is found to be the highest near the eutectic point and is nearly five times that for the pure fluid, which slows down the nucleation rate by a factor of 10(-31). These free energy barriers are some of highest ever computed using simulations. For most of the conditions studied, the composition of the critical nucleus corresponds to either one of the two thermodynamically stable solid phases. However, near the eutectic point, the nucleation barrier is lowest for the formation of the metastable random hexagonal closed packed (rhcp) solid phase with composition lying in the two-phase region of the phase diagram. The fluid to solid phase transition is hypothesized to proceed via formation of a metastable rhcp phase followed by a phase separation into respective stable fcc solid phases.

Communication: Virial coefficients and demixing in highly asymmetric binary additive hard-sphere mixtures

The problem of demixing in a binary fluid mixture of highly asymmetric additive hard spheres is revisited. A comparison is presented between the results derived previously using truncated virial expansions for three finite size ratios with those that one obtains with the same approach in the extreme case in which one of the components consists of point particles. Since this latter system is known not to exhibit fluid-fluid segregation, the similarity observed for the behavior of the critical constants arising in the truncated series in all instances, while not being conclusive, may cast serious doubts as to the actual existence of a demixing fluid-fluid transition in disparate-sized binary additive hard-sphere mixtures.

Effects of Sugars on the Thermal Stability of a Protein

It is experimentally known that the heat-denaturation temperature of a protein is raised by sugar addition [1]. In earlier work [2], we proposed a measure of the thermal stability of a protein, which is defined as the solvent-entropy gain at 298 K upon protein folding ΔS normalized by the number of residues. ΔS was calculated using a hybrid method of the angle-dependent integral equation theory combined with the mulipolar water model and the morphometric approach. Here we show that ΔS remains effective even when the model water is replaced by the hard-sphere solvent whose number density and molecular diameter are set at those of water. We then investigate the effects of sugar addition on the thermal stability by considering water-sugar solution modeled as a binary mixture of hard spheres. The thermal stability is determined by a complex interplay of the molecular size of the sugar D and the total packing fraction of the solution η. D is estimated from the volume per molecule in the sugar crystal, and η is calculated using the experimental data of the solution density. A finding is that the protein is more stabilized as the sucrose or glucose concentration becomes higher and the stabilization effect is stronger for sucrose than for glucose. This is in accord with the experimental observations [1]. We analyze the contributions from the protein-solvent pair and many-body correlations to enhancement of the thermal stability. The contribution from the many-body correlation becomes stronger as the degree of thermal-stability enhancement increases, suggesting that the solvent crowding is made more serious by sugar addition, leading to an increase in the solvent-entropy gain upon folding.[1] J. F. Back, Biochemistry 18 (1979) 5191.[2] K. Oda et al., J. Chem. Phys. 134 (2011) 025101.

Yielding of binary colloidal glasses

The rheological response, in particular the non-linear response, to oscillatory shear is experimentally investigated in colloidal glasses. The glasses are highly concentrated binary hard-sphere mixtures with relatively large size disparities. For a size ratio of 0.2, a strong reduction of the normalized elastic moduli, the yield strain and stress and, for some samples, even melting of the glass to a fluid is observed upon addition of the second species. This is attributed to the more efficient packing, as indicated by the shift of random close packing to larger total volume fractions. This leads to an increase in free volume which favours cage deformations and hence a loosening of the cage. Cage deformations are also favoured by the structural heterogeneity introduced by the second species. For a limited parameter range, we furthermore found indications of two-step yielding, as has been reported previously for attractive glasses. In samples containing spheres with more comparable sizes, namely a size ratio of 0.38, the cage seems less distorted and structural heterogeneities on larger length scales seem to become important. The limited structural changes are reflected in only a small reduction of the moduli, yield strain and stress.

Recent developments in classical density functional theory: Internal energy functional and diagrammatic structure of fundamental measure theory

An overview of several recent developments in density functional theory for classical inhomogeneous liquids is given. We show how Levy's constrained search method can be used to derive the variational principle that underlies density functional theory. An advantage of the method is that the Helmholtz free energy as a functional of a trial one-body density is given as an explicit expression, without reference to an external potential as is the case in the standard Mermin-Evans proof by reductio ad absurdum. We show how to generalize the approach in order to express the internal energy as a functional of the one-body density distribution and of the local entropy distribution. Here the local chemical potential and the bulk temperature play the role of Lagrange multipliers in the Euler-Lagrange equations for minimiziation of the functional. As an explicit approximation for the free-energy functional for hard sphere mixtures, the diagrammatic structure of Rosenfeld's fundamental measure density unctional is laid out. Recent extensions, based on the Kierlik-Rosinberg scalar weight functions, to binary and ternary non-additive hard sphere mixtures are described.

Self-assembly of colloidal particles into strings in a homogeneous external electric or magnetic field

Colloidal particles with a dielectric constant (magnetic susceptibility) mismatch with the surrounding solvent acquire a dipole moment in a homogeneous external electric (magnetic) field. The resulting dipolar interactions can lead to aggregation of the particles into string-like clusters. Recently, several methods have been developed to make these structures permanent. However, especially when multiple particle sizes and/or more complex shapes than single spheres are used, the parameter space for these experiments is enormous. We therefore use Monte Carlo simulations to investigate the structure of the self-assembled string-like aggregates in binary mixtures of dipolar hard and charged spheres, as well as dipolar hard asymmetric dumbbells. Binary mixtures of spheres aggregate in different types of clusters depending on the size ratio of the spheres. For highly asymmetric systems, the small spheres form ring-like and flame-like clusters around strings of large spheres, while for size ratios closer to 1, alternating strings of both large and small spheres are observed. For asymmetric dumbbells, we investigate both the effect of size ratio and dipole moment ratio, leading to a large variety of cluster shapes, including chiral clusters.

Single file and normal dual mode diffusion in highly confined hard sphere mixtures under flow

We use Monte Carlo simulations to study the dual-mode diffusion regime of binary and tertiary mixtures of hard spheres confined in narrow cylindrical pores under the influence of an imposed flow. The flow is introduced to the dynamics by adding a small bias directed along the long axis of the pore to the random displacement of each Monte Carlo move. As a result, the motion of the particles in all the components is dominated by a drift velocity that causes the mean squared displacements to increase quadratically in the long time limit. However, an analysis of the mean squared displacements at intermediate time scales shows that components of the mixture above and below their passing thresholds still exhibit behaviors consistent with normal and single-file diffusion, respectively. The difference between the mean squared displacements of the various components is shown to go though a maximum, suggesting there may be an optimal pore diameter for the separation of mixtures exhibiting dual-mode diffusion.

Phase diagram of hard snowman-shaped particles

We present the phase diagram of hard snowman-shaped particles calculated using Monte Carlo simulations and free energy calculations. The snowman particles consist of two hard spheres rigidly attached at their surfaces. We find a rich phase behavior with isotropic, plastic crystal, and aperiodic crystal phases. The crystalline phases found to be stable for a given sphere diameter ratio correspond mostly to the close packed structures predicted for equimolar binary hard-sphere mixtures of the same diameter ratio. However, our results also show several crystal-crystal phase transitions, with structures with a higher degree of degeneracy found to be stable at lower densities, while those with the best packing are found to be stable at higher densities.

Demixing and field-induced population inversion in a mixture of neutral and dipolar-hard spheres confined in a slit pore

We study the influence of an external field on demixing and its interplay with the field-induced population inversion for a binary mixture of neutral and dipolar non-additive hard-spheres confined in a slit pore. Demixing lines are determined by Gibbs Ensemble Monte Carlo simulations and population inversion paths by grand-canonical/canonical simulations of the pore/bulk equilibrium. Besides the demixing line in the bulk, results are given for two different pore widths and in parallel and normal fields. Similar to the effect of geometrical confinement, a normal field is found to favour the mixed state so that the population inversion does not interfere with demixing. A parallel field leads to more complex scenarios.

Field induced gradient simulations: A high throughput method for computing chemical potentials in multicomponent systems

We present a simulation method for direct computation of chemical potentials in multicomponent systems. The method involves application of a field to generate spatial gradients in the species number densities at equilibrium, from which the chemical potential of each species is theoretically estimated. A single simulation yields results over a range of thermodynamic states, as in high throughput experiments, and the method remains computationally efficient even at high number densities since it does not involve particle insertion at high densities. We illustrate the method by Monte Carlo simulations of binary hard sphere mixtures of particles with different sizes in a gravitational field. The results of the gradient Monte Carlo method are found to be in good agreement with chemical potentials computed using the classical Widom particle insertion method for spatially uniform systems.

Polymer-enforced crystallization of a eutectic binary hard sphere mixture

We prepared a buoyancy matched binary mixture of polydisperse polystyrene microgel spheres of size ratio Γ = 0.785 at a volume fraction of Φ = 0.567 just below the kinetic glass transition. In line with theoretical expectations, a eutectic phase behaviour was observed, but only a minor fraction of the samples crystallized at all. By adding a short non-adsorbing polymer we enforce inter-species fractionation into coexisting pure component crystals, which in turn also shows signs of intra-species fractionation. We show that in formerly inaccessible regions of the phase diagram binary hard sphere physics are made observable using attractive hard spheres.

Depletion potentials in highly size-asymmetric binary hard-sphere mixtures: Comparison of simulation results with theory

We report a detailed study, using state-of-the-art simulation and theoretical methods, of the effective (depletion) potential between a pair of big hard spheres immersed in a reservoir of much smaller hard spheres, the size disparity being measured by the ratio of diameters q ≡ σ(s)/σ(b). Small particles are treated grand canonically, their influence being parameterized in terms of their packing fraction in the reservoir η(s)(r). Two Monte Carlo simulation schemes--the geometrical cluster algorithm, and staged particle insertion--are deployed to obtain accurate depletion potentials for a number of combinations of q ≤ 0.1 and η(s)(r). After applying corrections for simulation finite-size effects, the depletion potentials are compared with the prediction of new density functional theory (DFT) calculations based on the insertion trick using the Rosenfeld functional and several subsequent modifications. While agreement between the DFT and simulation is generally good, significant discrepancies are evident at the largest reservoir packing fraction accessible to our simulation methods, namely, η(s)(r) = 0.35. These discrepancies are, however, small compared to those between simulation and the much poorer predictions of the Derjaguin approximation at this η(s)(r). The recently proposed morphometric approximation performs better than Derjaguin but is somewhat poorer than DFT for the size ratios and small-sphere packing fractions that we consider. The effective potentials from simulation, DFT, and the morphometric approximation were used to compute the second virial coefficient B(2) as a function of η(s)(r). Comparison of the results enables an assessment of the extent to which DFT can be expected to correctly predict the propensity toward fluid-fluid phase separation in additive binary hard-sphere mixtures with q ≤ 0.1. In all, the new simulation results provide a fully quantitative benchmark for assessing the relative accuracy of theoretical approaches for calculating depletion potentials in highly size-asymmetric mixtures.

Analytical behavior of the fourth and fifth virial coefficients of a hard-sphere mixture

This paper focus on the study of the composition-dependent fourth and fifth virial coefficient of a hard-sphere binary mixture, namely, B(4)(s) and B(5)(s). On one side, the analytical expression of B(4)(s) is revised. In particular, I analyzed the composition-independent term B(4)[1](s) included in B(4)(s) and found a simplified form of its exact expression, which has the advantage over that previously published of highlighting the geometric properties of this term. On the other side, using a geometrical approach, I found a set of nonanalytic points of B(4)(s) and B(5)(s) as functions of s by analyzing each of their composition-independent terms.