Hard-core Repulsion Research Articles

Nontoxic colloidal particles impede antibiotic resistance of swarming bacteria by disrupting collective motion and speed.

A monolayer of swarming B. subtilis on semisolid agar is shown to display enhanced resistance against antibacterial drugs due to their collective behavior and motility. The dynamics of swarming motion, visualized in real time using time-lapse microscopy, prevents the bacteria from prolonged exposure to lethal drug concentrations. The elevated drug resistance is significantly reduced when the collective motion of bacteria is judiciously disrupted using nontoxic polystyrene colloidal particles immobilized on the agar surface. The colloidal particles block and hinder the motion of the cells, and force large swarming rafts to break up into smaller packs in order to maneuver across narrow spaces between densely packed particles. In this manner, cohesive rafts rapidly lose their collectivity, speed, and group dynamics, and the cells become vulnerable to the drugs. The antibiotic resistance capability of swarming B. subtilis is experimentally observed to be negatively correlated with the number density of colloidal particles on the engineered surface. This relationship is further tested using an improved self-propelled particle model that takes into account interparticle alignment and hard-core repulsion. This work has pertinent implications on the design of optimal methods to treat drug resistant bacteria commonly found in swarming colonies.

Effective stochastic generators for conditioned dynamics at an atypical reaction-diffusion current.

We consider the fluctuations of a time-integrated particle current around an atypical value in a generic stochastic Markov process involving classical particles with two-site interaction and hard-core repulsion on a finite one-dimensional lattice with open boundaries. We address the question of which interactions one has to impose on such a process to make the atypical value of the current typical. It is known that a corresponding effective stochastic Markov process might exist whose typical current value is equal to the atypical current value in the original process within a time-translational invariant regime. This effective process has, in principle, nonlocal transition rates. Nevertheless, it turns out that under some conditions, the stochastic generator of the effective process has the same dynamical rules as the stochastic generator of the original process. We find these conditions and show that our approach can be generalized to any time-integrated observable.

Mechanically-driven spreading of bacterial populations

The effect of mechanical interactions between cells in the spreading of bacterial populations was investigated in one-dimensional space. A continuum-mechanics approach, comprising cell migration, proliferation, and exclusion processes, was employed to elucidate the dynamics. The consequent nonlinear reaction-diffusion-like equation describes the constitution dynamics of a bacterial population. In this model, bacterial cells were treated as rod-like particles that interact with each other through hard-core repulsion, which introduces the exclusion effect that causes bacterial populations to migrate quickly at high density. The propagation of bacterial density as a traveling wave front over extended times was also analyzed. The analytical and numerical solutions revealed that the front speed was enhanced by the exclusion process, which depended upon the cell-packing fraction. Finally, we qualitatively compared our theoretical results with experimental evidence.

Tables of equation-of-state, thermodynamic properties, and shock Hugoniot for hot dense fluid deuterium

We present computational results and tables of the equation-of-state, thermodynamic properties, and shock Hugoniot for hot dense fluid deuterium. The present results are generated using a recently developed chemical model that takes into account different high density effects such as Coulomb interactions among charged particles, partial degeneracy, and intensive short range hard core repulsion. Internal partition functions are evaluated in a statistical-mechanically consistent way implementing recent developments in the literature. The shock Hugoniot curve derived from the present tables is overall in reasonable agreement with the Hugoniot derived from the Nova-laser shock wave experiments on liquid deuterium, showing that deuterium has a significantly higher compressibility than predicted by the SESAME tables or by Path Integral Monte Carlo calculations. Computational results are presented as surface plots for the dissociated fraction, degree of ionization, pressure, and specific internal energy for densities ranging from 0.0001 to 40 g/cm3 and temperatures from 2000 to ∼106 K. Tables for values of the above mentioned quantities in addition to the specific heat at constant pressure, cp, ratio of specific heats, cp/cv, sound speed and Hugoniot curve (for a specific initial state) are presented for practical use.

Mean-field approach in the multi-component gas of interacting particles applied to relativistic heavy-ion collisions

A generalized mean-field approach for the thermodynamic description of relativistic single- and multi-component gas in the grand canonical ensemble is formulated. In the framework of the proposed approach, different phenomenological excluded-volume procedures are presented and compared to the existing ones. The mean-field approach is then used to effectively include hard-core repulsion in hadron-resonance gas model for description of chemical freeze-out in heavy-ion collisions. We calculate the collision energy dependence of several quantities for different values of hard-core hadron radius and for different excluded-volume procedures such as the van der Waals and Carnahan–Starling models. It is shown that a choice of the excluded-volume model becomes important for large particle densities. For large enough values of hadron radii ( fm) there can be a sizable difference between different excluded-volume procedures used to describe the chemical freeze-out in heavy-ion collisions. At the same time, for the smaller and more commonly used values of hard-core hadron radii ( fm), the precision of the van der Waals excluded-volume procedure is shown to be sufficient.

Large deviation function of a tracer position in single file diffusion

Diffusion of impenetrable particles in a crowded one-dimensional channel is referred as the single file diffusion. The particles do not pass each other and the displacement of each individual particle is sub-diffusive. We analyse a simple realization of this single file diffusion problem where one dimensional Brownian point particles interact only by hard-core repulsion. We show that the large deviation function which characterizes the displacement of a tracer at large time can be computed via a mapping to a problem of non-interacting Brownian particles. We confirm recently obtained results of the one time distribution of the displacement and show how to extend them to the multi-time correlations. The probability distribution of the tracer position depends on whether we take annealed or quenched averages. In the quenched case we notice an exact relation between the distribution of the tracer and the distribution of the current. This relation is in fact much more general and would be valid for arbitrary single file diffusion. It allows in particular to get the full statistics of the tracer position for the symmetric simple exclusion process (SSEP) at density 1/2 in the quenched case.

Phase transitions in strongly interacting matter

I discuss the phase structure of hadronic matter in terms of the basic dynamical and geometrical features of hadrons. Increasing the density of constituents of finite spatial extension, by increasing the temperature T or the baryochemical potential µ, eventually “fills the box” and eliminates the physical vacuum. The corresponding transition as function of T and µ can be determined through percolation theory. At low baryon density, this means a fusion of overlapping mesonic bags to one large bag, while at high baryon density, hard core repulsion restricts the spatial mobility of baryons. As a consequence, there are two distinct limiting regimes for hadronic matter.

Validity of the Spin-Wave Approximation for the Free Energy of the Heisenberg Ferromagnet

We consider the quantum ferromagnetic Heisenberg model in three dimensions, for all spins $S\geq 1/2$. We rigorously prove the validity of the spin-wave approximation for the excitation spectrum, at the level of the first non-trivial contribution to the free energy at low temperatures. Our proof comes with explicit, constructive upper and lower bounds on the error term. It uses in an essential way the bosonic formulation of the model in terms of the Holstein-Primakoff representation. In this language, the model describes interacting bosons with a hard-core on-site repulsion and a nearest-neighbor attraction. This attractive interaction makes the lower bound on the free energy particularly tricky: the key idea there is to prove a differential inequality for the two-particle density, which is thereby shown to be smaller than the probability density of a suitably weighted two-particle random process on the lattice.

Hierarchical self-assembly of nanoparticles in polymer matrix and the nature of the interparticle interaction.

Using small angle X-ray scattering (SAXS), we elucidated the spatial organization of palladium (Pd) nanoparticles (NPs) in the polymer matrix of poly(2-vinylpyridine) (P2VP) and the nature of inter-nanoparticle interactions, where the NPs were synthesized in the presence of P2VP by the reduction of palladium acetylacetonate (Pd(acac)2). The experimental SAXS profiles were analysed on the basis of a hierarchical structure model considering the following two types of interparticle potential: (i) hard-core repulsion only (i.e., the hard-sphere interaction) and (ii) hard-core repulsion together with an attractive potential well (i.e., the sticky hard-sphere interaction). The corresponding theoretical scattering functions, which were used for analysing the experimental SAXS profiles, were obtained within the context of the Percus-Yevick closure and the Ornstein-Zernike equation in the fundamental liquid theory. The analyses revealed that existence of the attractive potential well is indispensable to account for the experimental SAXS profiles. Moreover, the morphology of the hybrids was found to be characterized by a hierarchical structure with three levels, where about six primary NPs with the diameter of ca. 1.8 nm (level one) formed local clusters (level two), and these clusters aggregated to build up a large-scale mass-fractal structure (level three) with the fractal dimension of ca. 2.3. The scattering function developed here is of general use for quantitatively characterizing the morphological structures of polymer/NP hybrids and, in particular, for exploring the interaction potential of the NPs on the basis of the fundamental liquid theory.

Dissociation and ionization equilibria of deuterium fluid over a wide range of temperatures and densities

We investigate the dissociation and ionization equilibria of deuterium fluid over a wide range of temperatures and densities. The partition functions for molecular and atomic species are evaluated, in a statistical-mechanically consistent way, implementing recent developments in the literature and taking high-density effects into account. A new chemical model (free energy function) is introduced in which the fluid is considered as a mixture of diatomic molecules, atoms, ions and free electrons. Intensive short range hard core repulsion is taken into account together with partial degeneracy of free electrons and Coulomb interactions among charged particles. Samples of computational results are presented as a set of isotherms for the degree of ionization, dissociated fraction of molecules, pressure, and specific internal energy for a wide range of densities and temperatures. Predictions from the present model calculations show an improved and sensible physical behavior compared to other results in the literature.

Heat conduction in a chain of dissociating particles: Effect of dimensionality.

The paper considers heat conduction in a model chain of composite particles with hard core and elastic external shell. Such model mimics three main features of realistic interatomic potentials--hard repulsive core, quasilinear behavior in a ground state, and possibility of dissociation. It has become clear recently that this latter feature has crucial effect on convergence of the heat conduction coefficient in thermodynamic limit. We demonstrate that in one-dimensional chain of elastic particles with hard core the heat conduction coefficient also converges, as one could expect. Then we explore effect of dimensionality on the heat transport in this model. For this sake, longitudinal and transversal motions of the particles are allowed in a long narrow channel. With varying width of the channel, we observe sharp transition from "one-dimensional" to "two-dimensional" behavior. Namely, the heat conduction coefficient drops by about order of magnitude for relatively small widening of the channel. This transition is not unique for the considered system. Similar phenomenon of transition to quasi-1D behavior with growth of aspect ratio of the channel is observed also in a gas of densely packed hard (billiard) particles, both for two- and three-dimensional cases. It is the case despite the fact that the character of transition in these two systems is not similar, due to different convergence properties of the heat conductivity. In the billiard model, the divergence pattern of the heat conduction coefficient smoothly changes from logarithmic to power-like law with increase of the length.

Structures of simple liquids in contact with nanosculptured surfaces.

We present a density functional study of Lennard-Jones liquids in contact with a nanocorrugated wall. The corresponding substrate potential is taken to exhibit a repulsive hard core and a Van der Waals attraction. The corrugation is modeled by a periodic array of square nanopits. We have used the modified Rosenfeld density functional in order to study the interfacial structure of these liquids which with respect to their thermodynamic bulk state are considered to be deep inside their liquid phase. We find that already considerably below the packing fraction of bulk freezing of these liquids, inside the nanopits a three-dimensional-like density localization sets in. If the sizes of the pits are commensurate with the packing requirements, we observe high-density spots separated from each other in all spatial directions by liquid of comparatively very low density. The number, shape, size, and density of these high-density spots depend sensitively on the depth and width of the pits. Outside the pits, only layering is observed; above the pit openings these layers are distorted with the distortion reaching up to a few molecular diameters. We discuss quantitatively how this density localization is affected by the geometrical features of the pits and how it evolves upon increasing the bulk packing fraction. Our results are transferable to colloidal systems and pit dimensions corresponding to several diameters of the colloidal particles. For such systems the predicted unfolding of these structural changes can be studied experimentally on much larger length scales and more directly (e.g., optically) than for molecular fluids which typically call for sophisticated x-ray scattering.

Thermodynamic mechanism of the density anomaly of liquid water

Although density anomaly of liquid water has long been studied by many different authors up to now, it is not still cleared what thermodynamic mechanism induces the anomaly. The thermodynamic properties of substances are determined by interparticle interactions. We analyze what characteristics of pair potential cause the density anomaly on the basis of statistical mechanics and thermodynamics using a thermodynamically self-consistent Ornstein-Zernike approximation (SCOZA). We consider a fluid of spherical particles with a pair potential given by a hard-core repulsion plus a soft-repulsion and an attraction. We show that the density anomaly occurs when the value of the soft-repulsive potential at hard-core contact is in some proper range, and the range depends on the attraction. Further, we show that the behavior of the excess internal energy plays an essential role in the density anomaly and the behavior is mainly determined by the values of the soft-repulsive potential, especially near the hard core contact. Our results show that most of ideas put forward up to now are not the direct causes of the density anomaly of liquid water.

Entropic depletion in colloidal suspensions and polymer liquids: role of nanoparticle surface topography.

We employ a hybrid Monte Carlo plus integral equation theory approach to study how dense fluids of small nanoparticles or polymer chains mediate entropic depletion interactions between topographically rough particles where all interaction potentials are hard core repulsion. The corrugated particle surfaces are composed of densely packed beads which present variable degrees of controlled topographic roughness and free volume associated with their geometric crevices. This pure entropy problem is characterized by competing ideal translational and (favorable and unfavorable) excess entropic contributions. Surface roughness generically reduces particle depletion aggregation relative to the smooth hard sphere case. However, the competition between ideal and excess packing entropy effects in the bulk, near the particle surface and in the crevices, results in a non-monotonic variation of the particle-monomer packing correlation function as a function of the two dimensionless length scale ratios that quantify the effective surface roughness. As a result, the inter-particle potential of mean force (PMF), second virial coefficient, and spinodal miscibility volume fraction vary non-monotonically with the surface bead to monomer diameter and particle core to surface bead diameter ratios. A miscibility window is predicted corresponding to an optimum degree of surface roughness that completely destroys depletion attraction resulting in a repulsive PMF. Variation of the (dense) matrix packing fraction can enhance or suppress particle miscibility depending upon the amount of surface roughness. Connecting the monomers into polymer chains destabilizes the system via enhanced contact depletion attraction, but the non-monotonic variations with surface roughness metrics persist.

Аномальная сверхпроводимость и сверхтекучесть в фермионных системах с отталкиванием

We discuss the mechanisms of unconventional superconductivity and superfluidity in 3D and 2D fermionic systems with purely repulsive interaction at low densities. We construct phase diagrams of these systems and find the areas of the superconducting state in free space, as well as on the lattice in the framework of the Fermi-gas model with hard-core repulsion, the Hubbard model, the Shubin-Vonsovsky model, and the $t-J$ model. We demonstrate that the critical superconducting temperature can be greatly increased in the spin-polarized case or in a two-band situation already at low densities. The proposed theory is based on the Kohn-Luttinger mechanism or its generalizations and explains or predicts anomalous $p$-, $d$-, and $f$-wave pairing in various materials, such as high-temperature superconductors, the idealized monolayer and bilayer of doped graphene, heavy-fermion systems, layered organic superconductors, superfluid $^3$He, spin-polarized $^3$He mixtures in $^4$He, ultracold quantum gases in magnetic traps, and optical lattices.

Enthalpy Mediated Protein Stabilization by Macromolecular Crowding

Understanding the structure and stability of biomolecules in the cellular environment requires knowledge of their interplay with high concentrations of macromolecules, osmolytes, salts and membranes. The macromolecular crowding effect in a cell is usually described by the excluded volume theory based on hardcore repulsions [1]. However, recent studies emphasize the role of further contributions aside from a pure volume effect including enthalpic and solvent effects [2, 3]. We study cosolute effects at high molecular and macromolecular concentrations via a thermodynamic analysis of the thermal unfolding of ubiquitin in the presence of different concentrations of cosolutes (glucose, dextran, poly(ethylene glycol), potassium chloride) [4]. In contrast to the excluded volume theory, we observed enthalpic stabilization and entropic destabilization forces for all tested cosolutes. The enthalpic stabilization mechanism of ubiquitin in macromolecular polysaccharide solutions of dextran was thereby similar to the effects observed in monomeric glucose. The more hydrophobic polymer polyethylene glycol destabilizes native ubiquitin, presumably via unspecific direct interactions with the protein. Thereby, the macromolecular character of PEG and dextran - and hence its excluded volume - is not to the determining factor which influences the folding equilibrium of ubiquitin. Instead, our data suggest a key role for hydration water molecules in the interaction of proteins and cosolutes.

Nematic and lamellar liquid-crystalline phases in suspensions of charged silica-coated gibbsite platelets

Computer simulations, theoretical investigations and experiments carried out over the last 20 years have demonstrated that suspensions of hard plate-like colloids display a rich liquid-crystal phase behaviour including nematic and columnar phases. Recently, it has become clear that charged colloidal platelets display an even richer phase behaviour including smectic A and smectic B phases. Here, we report on the formation of liquid crystals in suspensions of charged silica-coated gibbsite platelets in dimethylformamide in the presence of 1 mM salt and without added salt. A nematic phase is observed in the system with added salt, while in the system without added salt a lamellar (smectic A) liquid-crystalline phase is formed as demonstrated by optical observations and synchrotron small angle X-ray scattering measurements. The observed phases are in contrast with the columnar phase that would be expected if the platelets were interacting through hard-core repulsions. A bifurcation analysis suggests that, on decreasing ionic strength, first the columnar phase is destabilised in favour of nematic order, which in turn is destabilised in favour of lamellar order. Our experimental and theoretical results support the suggestion that the appearance of nematic and lamellar phases is related to the strength and range of the double-layer repulsion.

Nonmonotonic diffusion of particles among larger attractive crowding spheres.

We study the diffusive motion of particles among fixed spherical crowders. The diffusers interact with the crowders through a combination of a hard-core repulsion and a short-range attraction. The long-time effective diffusion coefficient of the diffusers is found to depend nonmonotonically on the strength of their attraction to the crowders. That is, for a given concentration of crowders, a weak attraction to the crowders enhances diffusion. We show that this counterintuitive fact can be understood in terms of the mesoscopic excess chemical potential landscape experienced by the diffuser. The roughness of this excess chemical potential landscape quantitatively captures the nonmonotonic dependence of the diffusion rate on the strength of crowder-diffuser attraction; thus, it is a purely static predictor of dynamic behavior. The mesoscopic view given here provides a unified explanation for enhanced diffusion effects that have been found in various systems of technological and biological interest.

Collective translational and rotational Monte Carlo cluster move for general pairwise interaction.

Virtual move Monte Carlo is a cluster algorithm which was originally developed for strongly attractive colloidal, molecular, or atomistic systems in order to both approximate the collective dynamics and avoid sampling of unphysical kinetic traps. In this paper, we present the algorithm in the form, which selects the moving cluster through a wider class of virtual states and which is applicable to general pairwise interactions, including hard-core repulsion. The newly proposed way of selecting the cluster increases the acceptance probability by up to several orders of magnitude, especially for rotational moves. The results have their applications in simulations of systems interacting via anisotropic potentials both to enhance the sampling of the phase space and to approximate the dynamics.

On the potential of mean force of a sterically stabilized dispersion

The potential of mean force (PMF) is the total free energy of a many-body colloidal system, and consequently it includes all the interactions the colloids experience due to collisions with themselves and with the solvent. Here, the PMF of a colloidal dispersion under various circumstances of current interest, such as varying solvent quality, polymer coating thickness, and addition of electrostatic interaction, is obtained from radial distribution functions available from the literature. They are based on implicit-solvent, computer simulation studies of a model TiO2 dispersion that takes into account three major components to the interaction between colloidal particles, namely van der Waals attraction, repulsion between polymer coating layers, and a hard-core particle repulsion. In addition, a screened form of the electrostatic interaction was included. It is argued that optimal conditions for dispersion stability can be derived from a comparative analysis of the PMF under the different situations studied. This thermodynamics-based analysis is believed to be more accessible to specialists working on the development of improved colloidal formulations than that based on the more abstract, radial distribution functions.