Search

A simple model for functionalized disordered porous media is proposed and the effects of confinement on self-association, percolation and phase behavior of a fluid of patchy particles are studied. The media are formed by randomly distributed hard-sphere obstacles fixed in space and decorated by a certain number of off-center square-well sites. The properties of the fluid of patchy particles, represented by the fluid of hard spheres each bearing a set of the off-center square-well sites, are studied using an appropriate combination of the scaled particle theory for the porous media, Wertheim's thermodynamic perturbation theory, and Flory-Stockmayer theory. To assess the accuracy of the theory a set of computer simulations have been performed. In general, predictions of the theory appeared to be in good agreement with the computer simulation results. Confinement and competition between the formation of bonds connecting the fluid particles, and connecting fluid particles and obstacles of the matrix, gave rise to a re-entrant phase behavior with three critical points and two separate regions of the liquid-gas phase coexistence.

Protein molecules associate in solution, often in clusters beyond pairwise, leading to liquid phase separations and high viscosities. It is often impractical to study these multi-protein systems by atomistic computer simulations, particularly in multi-component solvents. Instead, their forces and states can be studied by liquid state statistical mechanics. However, past such approaches, such as the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, were limited to modeling proteins as spheres, and contained no microscopic structure-property relations. Recently, this limitation has been partly overcome by bringing the powerful Wertheim theory of associating molecules to bear on protein association equilibria. Here, we review these developments.

This study investigates the behaviour of a fluid of monoclonal antibodies (mAbs) when trapped in a confinement represented by rigid spherical obstacles that attract antibodies. The antibody molecule is depicted as an assembly of seven hard spheres (7-bead model), organized to resemble a Y -shaped object. The model antibody has two Fab and one Fc domains located in the corners of letter Y . In this calculation, only the Fab-Fab and Fab-Fc attractive pairs of interactions are effective. The confinement is formed by the randomly distributed hard-spheres fixed in space. The spherical obstacles, besides the size exclusion, interact with beads of the antibody molecules via the Yukawa attractive potential. We applied the combination of the scaled particle theory, replica Ornstein-Zernike equations, Wertheim's thermodynamic perturbation approach and the Flory-Stockmayer theory to calculate: (i) the phase diagram of the liquid-liquid phase separation and the percolation threshold, (ii) the cluster size distributions, and (iii) the second virial coefficient of the protein fluid distributed among the obstacles. All these quantities were calculated as functions of the strength of the attraction between the monoclonal antibodies, and the monoclonal antibodies and obstacles. The conclusion is that while the hard-sphere obstacles decrease the critical density and the critical temperature of the mAbs fluid, the effect of the protein-obstacle attraction is more complex. Adding an attractive potential to the obstacle-mAbs interaction first increases the wideness of the T *- ρ envelope. However, with the further increase of the obstacle-mAbs attraction intensity, we observe reversal of the effect, the T *- ρ curves become narrower. At some point, depending on the obstacle-mAbs interaction, the situation is observed where two different temperatures have the same fluid density (re-entry point). In all the cases shown here the critical point decreases below the value for the neat fluid, but the behaviour with respect to an increase of the strength of the obstacle-mAbs attraction is not monotonic. Yet another interesting phenomenon, known in the literature as an approach toward the "empty liquid" state, is observed. The stability of the "protein droplets", formed by the liquid-liquid phase separation, depends on their local environment and temperature.

Patchy colloids with three and four equivalent patches, confined in an attractive random porous medium, undergo re-entrant gas-liquid phase separation with the liquid phase density approaching zero at low temperatures. The (bonding) colloid-colloid interaction causes the liquid-gas phase separation, which is modulated by the presence of the randomly distributed hard-sphere obstacles, attracting the colloids via Yukawa potential. Due to this interaction, a layer of mutually bonded colloids around the obstacles is formed. The network becomes nonuniform, with colloid particles locally centered on the obstacles. Features described in this article may open possibilities to produce equilibrium gels with predefined nonuniform distribution of particles and indicate how complicated the phase behavior of biological macromolecules in a crowded environment may be.

Thermodynamic properties and structure of binary mixtures of patchy and spherical colloids are studied using a recently developed theory [Y. V. Kalyuzhnyi, et al., Soft Matter, 2020, 16, 3456]. The theory is based on a solution of the multidensity Ornstein-Zernike equation and provides completely analytical expressions for the structure factors of these systems and for all their major thermodynamical quantities. The considered mixtures are made up of particles of different size and with a different number of patches. A set of molecular simulation data has been generated to enable a systematic comparison and to access thus accuracy of the theoretical predictions. In general, the predictions of the theory appear to be in good agreement with computer simulation data. For the models with a lower number of patches (n p = 1, 2) the theoretical results show very good accuracy. Less accurate are the predictions for the four-patch versions of the model. While theoretical results for the radial distribution functions are, generally, relatively accurate for all the models, results for thermodynamics deteriorate with increasing concentration of the spherical colloids. Possible ways to improve the theory are briefly outlined.

This study is concerned with the behaviour of proteins within confinement created by hard-sphere obstacles. An individual antibody molecule is depicted as an assembly of seven hard spheres, organized to resemble a Y-shaped (on average) antibody (7-bead model) protein. For comparison with other studies we, in one case, model the protein as a hard sphere decorated by three short-range attractive sites. The antibody has two Fab and one Fc domains located in the corners of the letter Y. In this calculation, only the Fab-Fab and Fab-Fc attractive pair interactions are possible. The confinement is formed by the randomly distributed hard-sphere obstacles fixed in space. Aside from size exclusion, the obstacles do not interact with antibodies, but they affect the protein-protein correlation. We used a combination of the scaled-particle theory, Wertheim's thermodynamic perturbation theory and the Flory-Stockmayer theory to calculate: (i) the second virial coefficient of the protein fluid, (ii) the percolation threshold, (iii) cluster size distributions, and (iv) the liquid-liquid phase separation as a function of the strength of the various pair interactions of the protein and the model parameters, such as protein concentration and the packing fraction of obstacles. The conclusion is that hard-sphere obstacles strongly decrease the critical density and also, but to a much lesser extent, the critical temperature. Also, the confinement enhances clustering, making the percolating region broader. The effect depends on the model parameters, such as the packing fraction of obstacles η0, the inter-site interaction strength εIJ, and the ratio between the size of the obstacle σ0 and the size of one bead of the model antibody σhs; the value of this ratio is varied here from 2 to 5. Interestingly, at low to moderate packing fractions of obstacles, the second virial coefficient first slightly decreases (destabilization), and the slope depends on the observation temperature, but then at higher values of η0 it increases. The calculated values of the second virial coefficient also depend on the size of the obstacles.

An analytic theory for the structure and thermodynamics of two-component mixtures of patchy and spherical colloids is developed. The theory is based on an analytical solution of the multidensity Ornstein-Zernike equation supplemented by the associative Percus-Yevick closure relations. We derive closed-form analytic expressions for the partial structure factors and thermodynamic properties using the energy route for the model with arbitrary number of patches and any hard-sphere size ratio of the particles. To assess the accuracy of the theoretical predictions we compare them against existing and newly generated set of computer simulation data. In our numerical calculations we consider the model with equal hard-sphere sizes and one patch. Very good agreement between results of the theory and simulation for the pair correlation functions, excess internal energy and pressure is observed for almost all values of the system density, temperature and composition studied. Only in the region of low concentrations of spherical colloids the theoretical results become less accurate.

We present a theoretical study of colloidal stability of the model mixtures of monoclonal antibody molecules and non-adsorbing (no polymer-protein attraction) polymers. The antibodies are pictured as an assembly of seven hard spheres assuming a Y-like shape. Polymers present in the mixture are modeled as chain-like molecules having from 32 up to 128 monomers represented as hard spheres. We use Wertheim's thermodynamic perturbation theory to construct the two molecular species and to calculate measurable properties. The calculations are performed in the osmotic ensemble. In view that no direct attractive interaction is present in the model Hamiltonian, we only account for the entropic contribution to the phase equilibrium. We calculate chemical potentials and the equation of state for the model mixture to determine the liquid-liquid part of the phase diagram. We investigate how the critical antibody number density depends on the degree of polymerization and the bead size ratio of the polymer and protein components. The model mixture qualitatively correctly predicts some basic features of real systems. The effects of the model 'protein' geometry, that is the difference in results for the flexible Y-shaped protein versus the rigid spherical one, are also examined.

For biotechnological drugs, it is desirable to formulate antibody solutions with low viscosities. We go beyond previous colloid theories in treating protein-protein self-association of molecules that are antibody-shaped and flexible and have spatially specific binding sites. We consider interactions either through fragment antigen (Fab-Fab) or fragment crystalizable (Fab-Fc) binding. Wertheim's theory is adapted to compute the cluster-size distributions, viscosities, second virial coefficients, and Huggins coefficients, as functions of antibody concentration. We find that the aggregation properties of concentrated solutions can be anticipated from simpler-to-measure dilute solutions. A principal finding is that aggregation is controllable, in principle, through modifying the antibody itself, and not just the solution it is dissolved in. In particular: (i) monospecific antibodies having two identical Fab arms can form linear chains with intermediate viscosities. (ii) Bispecific antibodies having different Fab arms can, in some cases, only dimerize, having low viscosities. (iii) Arm-to-Fc binding allows for three binding partners, leading to networks and high viscosities.

Extension of Wertheim's thermodynamic perturbation theory and its combination with scaled particle theory is proposed and applied to study the liquid-gas phase behavior of polydisperse hard-sphere square-well chain fluid confined in the random porous media. Thermodynamic properties of the reference system, represented by the hard-sphere square-well fluid in the matrix, are calculated using corresponding extension of the second-order Barker-Henderson perturbation theory. We study effects of polydispersity and confinement on the phase behavior of the system. While polydispersity causes increase of the region of phase coexistence due to the critical temperature increase, confinement decreases the values of both critical temperature and critical density making the region of phase coexistence smaller. This effect is enhanced with the increase of the size ratio of the fluid and matrix particles. The increase of the average chain length at fixed values of polydispersity and matrix density shifts the critical point to a higher temperature and a slightly lower density.

We have studied the phase behavior of polydisperse Yukawa hard-sphere fluid confined in random porous media using extension and combination of high temperature approximation and scaled particle theory. The porous media are represented by the matrix of randomly placed hard-sphere obstacles. Due to the confinement, polydispersity effects are substantially enhanced. At an intermediate degree of fluid polydispersity and low density of the matrix, we observe two-phase coexistence with two critical points, and cloud and shadow curves forming closed loops of ellipsoidal shape. With the increase of the matrix density and the constant degree of polydispersity, these two critical points merge and disappear, and at lower temperatures the system fractionates into three coexisting phases. A similar phase behavior was observed in the absence of the porous media caused, however, by the increase of the polydispersity.

A simple model of dimerizing hard spheres with highly nontrivial fluid-solid phase behavior is proposed and studied using the recently proposed resummed thermodynamic perturbation theory for central force (RTPT-CF) associating potentials. The phase diagram has the fluid branch of the fluid-solid coexistence curve located at temperatures lower than those of the solid branch. This unusual behavior is related to the strong dependence of the system excluded volume on the temperature, which for the model at hand decreases with increasing temperature. This effect can be also seen for a wide family of fluid models with an effective interaction that combines short range attraction and repulsion at a larger distance. We expect that for sufficiently high repulsive barrier, such systems may show similar phase behavior.

The approach developed earlier to describe the dimerizing shielded attractive shell (SAS) primitive model of chemical association due to Cummings and Stell is generalized and extended to include a description of a polymerizing SAS model. Our extension is based on the combination of the resummed thermodynamic perturbation theory for central force (RTPT-CF) associating potential and self consistent scheme, which takes into account the changes in the system free volume due to association. Theoretical results for thermodynamical properties of the model at different bonding length, density and temperature are compared against newly generated computer simulation results. The theory gives very accurate predictions for the model with bonding length L (*) from the range 0  <  L (*)  <  0.6 at all values of the density and temperature studied, including the limit of infinitely large temperature.

We analyze the experimentally determined phase diagram of a γD-βB1 crystallin mixture. Proteins are described as dumbbells decorated with attractive sites to allow inter-particle interaction. We use thermodynamic perturbation theory to calculate the free energy of such mixtures and, by applying equilibrium conditions, also the compositions and concentrations of the co-existing phases. Initially we fit the Tcloudversus packing fraction η measurements for a pure (x2 = 0) γD solution in 0.1 M phosphate buffer at pH = 7.0. Another piece of experimental data, used to fix the model parameters, is the isotherm x2vs. η at T = 268.5 K, at the same pH and salt content. We use the conventional Lorentz-Berthelot mixing rules to describe cross interactions. This enables us to determine: (i) model parameters for pure βB1 crystallin protein and to calculate; (ii) complete equilibrium surface (Tcloud-x2-η) for the crystallin mixtures. (iii) We present the results for several isotherms, including the tie-lines, as also the temperature-packing fraction curves. Good agreement with the available experimental data is obtained. An interesting result of these calculations is evidence of the coexistence of three phases. This domain appears for the region of temperatures just out of the experimental range studied so far. The input parameters, leading good description of experimental data, revealed a large difference between the numbers of the attractive sites for γD and βB1 proteins. This interesting result may be related to the fact that γD has a more than nine times smaller quadrupole moment than its partner in the mixture.

Effects of addition of salts on stability of aqueous protein solutions are studied theoretically and the results are compared with experimental data. In our approach, all the interacting species, proteins, ions, and water molecules, are accounted for explicitly. Water molecules are modeled as hard spheres with four off-center attractive square-well sites. These sites serve to bind either another water or to solvate the ions or protein charges. The ions are represented as charged hard spheres, and decorated by attractive sites to allow solvation. Spherical proteins simultaneously possess positive and negative groups, represented by charged hard spheres, attached to the surface of the protein. The attractive square-well sites, mimicking the protein-protein van der Waals interaction, are located on the surface of the protein. To obtain numerical results, we utilized the energy route of Wertheim's associative mean spherical approximation. From measurable properties, we choose to calculate the second virial coefficient B2, which is closely related to the tendency of proteins to aggregate and eventually crystalize. Calculations are in agreement with experimental trends: (i) For low concentration of added salt, the alkali halide salts follow the inverse Hofmeister series. (ii) At higher concentration of added salt, the trend is reversed. (iii) When cations are varied, the salts follow the direct Hofmeister series. (iv) In contrast to the colloidal theories, our approach correctly predicts the non-monotonic behavior of B2 upon addition of salts. (v) With respect to anions, the theory predicts for the B2 values to follow different sequences below and above the iso-ionic point, as also confirmed experimentally. (vi) A semi-quantitative agreement between measured and calculated values for the second virial coefficient, as functions of pH of solution and added salt type and concentration, is obtained.

We propose an analytical solution of the multi-density Ornstein-Zernike equation supplemented by the associative Percus-Yevick closure relations specifically designed to describe the equilibrium properties of the novel class of patchy colloidal particles represented by the inverse patchy colloids with arbitrary number of patches. Using Baxter's factorization method, we reduce solution of the problem to the solution of one nonlinear algebraic equation for the fraction of the particles with one non-bonded patch. We present closed-form expressions for the structure (structure factor) and thermodynamic (internal energy) properties of the system in terms of this fraction (and parameters of the model). We perform computer simulation studies and compare theoretical and computer simulation predictions for the pair distribution function, internal energy, and number of single and double bonds formed in the system, for two versions of the model, each with two and three patches. We consider the models with formation of the double bonds blocked by the patch-patch repulsion and the models without patch-patch repulsion. In general very good agreement between theoretical and computer simulation results is observed.

Inverse patchy colloids (IPCs) differ from conventional patchy particles because their patches repel (rather than attract) each other and attract (rather than repel) the part of the colloidal surface that is free of patches. These particular features occur, e.g. in heterogeneously charged colloidal systems. Here we consider overall neutral IPCs carrying two, relatively small, polar patches. Previous studies of the same model under planar confinement have evidenced the formation of branched, disordered aggregates composed of ring-like structures. We investigate here the bulk behavior of the system via molecular dynamics simulations, focusing on both the structure and the dynamics of the fluid phase in a wide region of the phase diagram. Additionally, the simulation results for the static observables are compared to the Associative Percus Yevick solution of an integral equation approach based on the multi-density Ornstein-Zernike theory. A good agreement between theoretical and numerical quantities is observed even in the region of the phase diagram where the slowing down of the dynamics occurs.

Protein aggregation is broadly important in diseases and in formulations of biological drugs. Here, we develop a theoretical model for reversible protein-protein aggregation in salt solutions. We treat proteins as hard spheres having square-well-energy binding sites, using Wertheim's thermodynamic perturbation theory. The necessary condition required for such modeling to be realistic is that proteins in solution during the experiment remain in their compact form. Within this limitation our model gives accurate liquid-liquid coexistence curves for lysozyme and γ IIIa-crystallin solutions in respective buffers. It provides good fits to the cloud-point curves of lysozyme in buffer-salt mixtures as a function of the type and concentration of salt. It than predicts full coexistence curves, osmotic compressibilities, and second virial coefficients under such conditions. This treatment may also be relevant to protein crystallization.

We investigate the structural and thermodynamic properties of a new class of patchy colloids, referred to as inverse patchy colloids (IPCs) in their fluid phase via both theoretical methods and simulations. IPCs are nano- or micro- meter sized particles with differently charged surface regions. We extend conventional integral equation schemes to this particular class of systems: our approach is based on the so-called multi-density Ornstein-Zernike equation, supplemented with the associative Percus-Yevick approximation (APY). To validate the accuracy of our framework, we compare the obtained results with data extracted from NpT and NVT Monte Carlo simulations. In addition, other theoretical approaches are used to calculate the properties of the system: the reference hypernetted-chain (RHNC) method and the Barker-Henderson thermodynamic perturbation theory. Both APY and RHNC frameworks provide accurate predictions for the pair distribution functions: APY results are in slightly better agreement with MC data, in particular at lower temperatures where the RHNC solution does not converge.

The lack of a simple analytical description of the hard-sphere fluid in a matrix with hard-core obstacles is limiting progress in the development of thermodynamic perturbation theories for the fluid in random porous media. We propose a simple and highly accurate analytical scheme, which allows us to calculate thermodynamic and percolation properties of a network-forming fluid confined in the random porous media, represented by the hard-sphere fluid and overlapping hard-sphere matrices, respectively. Our scheme is based on the combination of scaled-particle theory, Wertheim's thermodynamic perturbation theory for associating fluids and extension of the Flory-Stockmayer theory for percolation. The liquid-gas phase diagram and percolation threshold line for several versions of the patchy colloidal fluid model confined in a random porous media are calculated and discussed. The method presented enables calculation of the thermodynamic and percolation properties of a large variety of polymerizing and network-forming fluids confined in random porous media.

We present a version of density functional approach for the system of patchy colloidal particles confined in slitlike pores with hard walls. Each particle possesses two off-center sites of the types A and B, and in addition to single A-A and B-B bonds, formation of the double A-B-A and B-A-B bonds is allowed. The proposed approach is based on the fundamental measure theory and the second order perturbation theory of Wertheim. For the model in question, a re-entrant phase behavior in a bulk system has been found [Kalyuzhnyi Y. V.; Cummings, P. T., J. Chem. Phys. 2013, 139, 104905] . Our calculations revealed that the re-entrant phase diagrams are also observed in confined systems. The upper critical temperature decreases with the pore width, while the lower critical temperature increases very slightly.

We propose an integral equation theory for a mixture of macroions, counterions, and co-ions in a waterlike fluid in which all the components are accounted for explicitly. The macroions can carry positive and negative surface charges simultaneously, mimicking in this way the situation occurring in protein solutions. To solve this complex model numerically, we utilize the associative mean spherical approximation, developed earlier for low-molecular-mass charge-symmetric electrolyte solutions. To illustrate the potential of this approach, we present numerical results for various experimental conditions. Among the measurable properties we choose to calculate the osmotic coefficient, a quantity that reflects the stability of the solution. We show that the osmotic coefficient depends not only on the magnitude of the net charge on the macroion but also on its sign, as well as on the nature of the low-molecular-mass electrolyte present. These specific ion effects are the consequence of differences in hydration between the ions in solution and charged groups on the macroion.

We propose a second-order thermodynamic perturbation theory for a hard-sphere patchy colloidal model with two doubly bondable patches of type A and B. AB bonding results in the formation of a three-dimensional network of the particles and AA and BB bonding promotes chain formation. The theory is applied to study the phase behaviour of the model at different values of the potential model parameters. Competition between network and chain formation gives rise to a re-entrant phase behaviour with upper and lower critical points. The model with an additional van der Waals type of interaction may have a re-entrant phase diagram with three critical points and two separate regions of the liquid-gas phase coexistence. We analyze our results in terms of the fractions of the particles in different bonding states and conclude that re-entrant phase coexistence can be seen as a coexistence between a gas phase rich in chain ends and a liquid phase rich in branch points.

We propose a second-order version of the resummed thermodynamic perturbation theory for patchy colloidal models with arbitrary number of multiply bondable patches. The model is represented by the hard-sphere fluid system with several attractive patches on the surface and resummation is carried out to account for blocking effects, i.e., when the bonding of a particle restricts (blocks) its ability to bond with other particles. The theory represents an extension of the earlier proposed first order resummed thermodynamic perturbation theory for central force associating potential and takes into account formation of the rings of the particles. In the limiting case of singly bondable patches (total blockage), the theory reduces to Wertheim thermodynamic perturbation theory for associating fluids. Closed-form expressions for the Helmholtz free energy, pressure, internal energy, and chemical potential of the model with an arbitrary number of equivalent doubly bondable patches are derived. Predictions of the theory for the model with two patches appears to be in a very good agreement with predictions of new NVT and NPT Monte Carlo simulations, including the region of strong association.

We propose an improved version of Wertheim's first order thermodynamic perturbation theory for the square-well m-point model of patchy colloids. Our version of the theory takes into account changes in the free volume of the system due to bond formation. The new theory is a significant improvement, giving good agreement with Monte Carlo simulations of the model.

A resummed thermodynamic perturbation theory for associating fluids with multiply bondable central force associating potential is extended for the fluid with multiple number of multiply bondable associating sites. We consider a multi-patch hard-sphere model for associating fluids. The model is represented by the hard-sphere fluid system with several spherical attractive patches on the surface of each hard sphere. Resummation is carried out to account for blocking effects, i.e., when the bonding of a particle restricts (blocks) its ability to bond with other particles. Closed form analytical expressions for thermodynamical properties (Helmholtz free energy, pressure, internal energy, and chemical potential) of the models with arbitrary number of doubly bondable patches at all degrees of the blockage are presented. In the limiting case of total blockage, when the patches become only singly bondable, our theory reduces to Wertheim's thermodynamic perturbation theory (TPT) for polymerizing fluids. To validate the accuracy of the theory we compare to exact values, for the thermodynamical properties of the system, as determined by Monte Carlo computer simulations. In addition we compare the fraction of multiply bonded particles at different values of the density and temperature. In general, predictions of the present theory are in good agreement with values for the model calculated using Monte Carlo simulations, i.e., the accuracy of our theory in the case of the models with multiply bondable sites is similar to that of Wertheim's TPT in the case of the models with singly bondable sites.

A resummed thermodynamic perturbation theory for associating fluids with multiply bondable central force associating potential is proposed. We consider a simple one-patch model for associating fluids. The model is represented by the hard-sphere system with a circular attractive patch on the surface of each hard-sphere. Resummation is carried out to account for the blocking effects, i.e., when the bonding of a particle restricts (blocks) its ability to bond with other particles. Closed form analytical expressions for thermodynamical properties (Helmholtz free energy, pressure, internal energy, and chemical potential) of the model with a doubly bondable patch at all degrees of the blockage are presented. In the limiting case of total blockage, when the particles become only singly bondable, our theory reduces to Wertheim's thermodynamic perturbation theory for dimerizing fluids. To validate the accuracy of the theory we compare to exact values, for the thermodynamical properties of the system, as determined by Monte Carlo computer simulations. In addition we compare the fraction of multiply bonded particles at different values of the density and temperature. Very good agreement between predictions of the theory, corrected for ring formation, and Monte Carlo computer simulation values was found in all cases studied. Less accurate are the original versions of the theory and Wertheim's thermodynamic perturbation theory for dimerization, especially at lower temperatures and larger sizes of the attractive patch.

We use the AMSA, associative mean spherical theory of associative fluids, to study ion-ion interactions in explicit water. We model water molecules as hard spheres with four off-center square-well sites and ions as charged hard spheres with sticky sites that bind to water molecules or other ions. We consider alkali halide salts. The choice of model parameters is based on two premises: (i) The strength of the interaction between a monovalent ion and a water molecule is inversely proportional to the ionic (crystal) diameter sigma(i). Smaller ions bind to water more strongly than larger ions do, taking into account the asymmetry of the cation-water and anion-water interactions. (ii) The number of contacts an ion can make is proportional to sigma2(i). In short, small ions bind waters strongly, but only a few of them. Large ions bind waters weakly, but many of them. When both a monovalent cation and anion are large, it yields a small osmotic coefficient of the salt, since the water molecules avoid the space in between large ions. On the other hand, salts formed from one small and one large ion remain hydrated and their osmotic coefficient is high. The osmotic coefficients, calculated using this model in combination with the integral equation theory developed for associative fluids, follow the experimental trends, including the unusual behavior of caesium salts.

An extension of the dimer version of Wertheim's thermodynamic perturbation theory is proposed and used to treat polydisperse mixture of the hard-sphere Yukawa chain fluid with chain length polydispersity. The structure and thermodynamic properties of the reference system, represented by multicomponent mixture of the Yukawa hard-sphere dimers, are described using polymer mean spherical approximation. Explicit analytical expressions for the Helmholtz free energy, chemical potential, and pressure in terms of the two chain length distribution function moments are derived. The theory is used to calculate the full liquid-gas phase diagram, including critical binodal, cloud and shadow curves, and distribution functions of the coexisting phases. Effects of fractionation in terms of the distribution function and its first and second moments are studied. Predictions of the theory for these effects are in qualitative agreement with the corresponding experimental predictions, obtained recently for the polydisperse mixture of polymers in a single solvent. In particular, both theory and experiment predict that longer chain polymers equilibrate to the liquid phase while shorter chain polymers are predominantly encountered in the gas phase.

We derive second-order thermodynamically consistent truncated composition expansions for the species residual partial molar properties--including volume, enthalpy, entropy, and Gibbs free energy--of dilute ternary systems aimed at the molecular account of solvation phenomena in compressible media. Then, we provide explicit microscopic interpretation of the expansion coefficients in terms of direct and total correlation function integrals over the microstructure of the corresponding infinite dilution reference system, as well as their pressure and temperature derivatives, allowing for the direct prediction of the species partial molar properties from the knowledge of the effective intermolecular interactions. Finally, we apply these formal results (a) to derive consistent expressions for the corresponding properties of the binary system counterparts, (b) to illustrate how the formal expressions converge, at the zero density limit, to those for multicomponent mixtures of imperfect gases obeying the virial equation of state Z = 1 + BPkT, and (c) to discuss, and highlight with examples from the literature, the thermodynamic inconsistencies encountered in the currently available first-order truncated expansions, by pinpointing the mathematical origin and physical meaning of the inconsistencies that render the first-order truncated expansions invalid.

A theoretical scheme developed earlier [Y. V. Kalyuzhnyi et al., Chem. Phys. Lett. 443, 243 (2007)] is used to calculate the full phase diagram of polydisperse athermal polymer-colloidal mixture with polydispersity in both colloidal and polymeric components. In the limiting case of bidisperse polymer-colloidal mixture, theoretical results are compared against computer simulation results. We present the cloud and shadow curves, critical binodals, and distribution functions of the coexisting phases and discuss the effects of polydispersity on their behavior. According to our analysis polydispersity extends the region of the phase instability, shifting the critical point to the lower values of the pressure and density. For the high values of the pressure polydispersity causes strong fractionation effects, with the large size colloidal particles preferring the low-density shadow phase and long chain length polymeric particles preferring the high-density shadow phase.

We previously applied Wertheim's thermodynamic perturbation theory for associative fluids to the simple Mercedes-Benz model of water. We found that the theory reproduced well the physical properties of hot water, but was less successful in capturing the more structured hydrogen bonding that occurs in cold water. Here, we propose an improved version of the thermodynamic perturbation theory in which the effective density of the reference system is calculated self-consistently. The new theory is a significant improvement, giving good agreement with Monte Carlo simulations of the model, and predicting key anomalies of cold water, such as minima in the molar volume and large heat capacity, in addition to giving good agreement with the isothermal compressibility and thermal expansion coefficient.

We recently developed an angle-dependent Wertheim integral equation theory (IET) of the Mercedes-Benz (MB) model of pure water [Silverstein et al., J. Am. Chem. Soc. 120, 3166 (1998)]. Our approach treats explicitly the coupled orientational constraints within water molecules. The analytical theory offers the advantage of being less computationally expensive than Monte Carlo simulations by two orders of magnitude. Here we apply the angle-dependent IET to studying the hydrophobic effect, the transfer of a nonpolar solute into MB water. We find that the theory reproduces the Monte Carlo results qualitatively for cold water and quantitatively for hot water.

The depletion interaction between proteins caused by addition of either uncharged or partially charged oligomers was studied using the canonical Monte Carlo simulation technique and the integral equation theory. A protein molecule was modeled in two different ways: either as (i) a hard sphere of diameter 30.0 A with net charge 0, or +5, or (ii) as a hard sphere with discrete charges (depending on the pH of solution) of diameter 45.4 A. The oligomers were pictured as tangentially jointed, uncharged, or partially charged, hard spheres. The ions of a simple electrolyte present in solution were represented by charged hard spheres distributed in the dielectric continuum. In this study we were particularly interested in changes of the protein-protein pair-distribution function, caused by addition of the oligomer component. In agreement with previous studies we found that addition of a nonadsorbing oligomer reduces the phase stability of solution, which is reflected in the shape of the protein-protein pair-distribution function. The value of this function in protein-protein contact increases with increasing oligomer concentration, and is larger for charged oligomers. The range of the depletion interaction and its strength also depend on the length (number of monomer units) of the oligomer chain. The integral equation theory, based on the Wertheim Ornstein-Zernike approach applied in this study, was found to be in fair agreement with Monte Carlo results only for very short oligomers. The computer simulations for a model mimicking the lysozyme molecule (ii) are in qualitative agreement with small-angle neutron experiments for lysozyme-dextran mixtures.

The structural and thermodynamic properties of a model solution containing flexible charged oligomers and an equivalent number of counterions were studied by means of the canonical Monte Carlo simulation and integral equation theory. The oligomers were represented as freely jointed chains of charged hard spheres. In accordance with the primitive model of electrolyte solutions, the counterions were modeled as charged hard spheres and the solvent as a dielectric continuum. Simulations were performed for a set of model parameters, independently varying the chain length and concentration of the oligomers. Structural properties in the form of pair distribution functions were calculated as functions of model parameters. In addition, thermodynamic properties such as the excess energy of solution and the excess chemical potential of counterions were obtained. These properties were correlated with the conformational averages of oligomers as reflected in the end-to-end distances and radii of gyration obtained from the simulations. The relation with the experimental data for heats of dilution and for the activity coefficient is discussed. Finally, theories based on Wertheim's integral equation approach (product reactant Ornstein-Zernike approach) [J. Stat. Phys. 42, 477 (1986)] in the so-called polymer mean spherical and polymer hypernetted chain approximations were tested against the new and existing computer simulations. For the values of parameters examined in this study, the integral equation theory yields semiquantitative agreement with computer simulations.

High temperature approximation (HTA) is used to describe the phase behavior of polydisperse multi-Yukawa hard-sphere fluid mixtures. It is demonstrated that in the frames of the HTA the model belongs to the class of "truncatable free energy models," i.e., the models with thermodynamical properties (Helmholtz free energy, chemical potential, and pressure) defined by the finite number of generalized moments. Using this property we were able to calculate the complete phase diagram (i.e., cloud and shadow curves as well as binodals) and size distribution functions of the coexisting phases of several different models of polydisperse fluids. In particular, we consider polydisperse one-Yukawa hard-sphere mixture with factorizable Yukawa coefficients and polydisperse Lennard-Jones (LJ) mixture with interaction energy parameter and/or size polydispersity. To validate the accuracy of the HTA we compare theoretical results with previously published results of more advanced mean spherical approximation (MSA) for the one-Yukawa model and with the Monte Carlo (MC) computer simulation results of [Wilding et al. J. Chem. Phys. 121, 6887 (2004); Phys. Rev. Lett. 95, 155701 (2005)] for the LJ model. We find that overall predictions of the HTA are in reasonable agreement with predictions of the MSA and MC, with the accuracy range from semiquantitative (for the phase diagram) to quantitative (for the size distribution functions).

The Blum-Hoye [J. Stat. Phys. 19 317 (1978)] solution of the mean spherical approximation for a multicomponent multi-Yukawa hard-sphere fluid is extended to a polydisperse multi-Yukawa hard-sphere fluid. Our extension is based on the application of the orthogonal polynomial expansion method of Lado [Phys. Rev. E 54, 4411 (1996)]. Closed form analytical expressions for the structural and thermodynamic properties of the model are presented. They are given in terms of the parameters that follow directly from the solution. By way of illustration the method of solution is applied to describe the thermodynamic properties of the one- and two-Yukawa versions of the model.

We have reconsidered the phase behavior of a polydisperse mixture of charged hard spheres (CHSs) introducing the concept of minimal size neutral clusters. We thus take into account ionic association effects observed in charged systems close to the phase boundary where the properties of the system are dominated by the presence of neutral clusters while the amount of free ions or charged clusters is negligible. With this concept we clearly pass beyond the simple level of the mean spherical approximation (MSA) that we have presented in our recent study of a polydisperse mixture of CHS [Yu. V. Kalyuzhnyi, G. Kahl, and P. T. Cummings, J. Chem. Phys. 120, 10133 (2004)]. Restricting ourselves to a 1:1 and possibly size-asymmetric model we treat the resulting polydisperse mixture of neutral, polar dimers within the framework of the polymer MSA, i.e., a concept that--similar as the MSA--readily can be generalized from the case of a mixture with a finite number of components to the polydisperse case: again, the model belongs to the class of truncatable free-energy models so that we can map the formally infinitely many coexistence equations onto a finite set of coupled, nonlinear equations in the generalized moments of the distribution function that characterizes the system. This allows us to determine the full phase diagram (in terms of binodals as well as cloud and shadow curves), we can study fractionation effects on the level of the distribution functions of the coexisting daughter phases, and we propose estimates on how the location of the critical point might vary in a polydisperse mixture with an increasing size asymmetry and polydispersity.

The distortion of structure of a simple, inverse-12, soft-disk fluid undergoing two-dimensional plane Couette flow was studied by nonequilibrium molecular dynamics (NEMD) simulation and by equilibrium Monte Carlo (MC) simulation with a nonequilibrium potential, under which the equilibrium structure of the fluid is that of the nonequilibrium fluid. Extension of the iterative predictor-corrector method of [Phys. Rev. A 33, 3451 (1986)]] was used to extract the nonequilibrium potential with the structure input from the NEMD simulation. Very good agreement for the structural properties and pressure tensor generated by the NEMD and MC simulation methods was found, thus providing the evidence that nonequilibrium liquid structure can be accurately reproduced via simple equilibrium simulations or theories using a properly chosen nonequilibrium potential. The method developed in the present study and numerical results presented here can be used to guide and test theoretical developments, providing them with the "experimental" results for the nonequilibrium potential.

The accuracy of several theories for the thermodynamic properties of the Yukawa hard-sphere chain fluid are studied. In particular, we consider the polymer mean spherical approximation (PMSA), the dimer version of thermodynamic perturbation theory (TPTD), and the statistical associating fluid theory for potentials of variable attractive range (SAFT-VR). Since the original version of SAFT-VR for Yukawa fluids is restricted to the case of one-Yukawa tail, we have extended SAFT-VR to treat chain fluids with two-Yukawa tails. The predictions of these theories are compared with Monte Carlo (MC) simulation data for the pressure and phase behavior of the chain fluid of different length with one- and two-Yukawa tails. We find that overall the PMSA and TPTD give more accurate predictions than SAFT-VR, and that the PMSA is slightly more accurate than TPTD., ((c) 2004 American Institute of Physics.)

Taking advantage of the availability of the analytic solution of the mean spherical approximation for a mixture of charged hard spheres with an arbitrary number of components we show that the polydisperse fluid mixture of charged hard spheres belongs to the class of truncatable free energy models, i.e., to those systems where the thermodynamic properties can be represented by a finite number of (generalized) moments of the distribution function that characterizes the mixture. Thus, the formally infinitely many equations that determine the parameters of the two coexisting phases can be mapped onto a system of coupled nonlinear equations in these moments. We present the formalism and demonstrate the power of this approach for two systems; we calculate the full phase diagram in terms of cloud and shadow curves as well as binodals and discuss the distribution functions of the coexisting daughter phases and their charge distributions., ((c) 2004 American Institute of Physics.)

The distortion of structure of a simple, inverse 12 soft-sphere fluid undergoing plane Couette flow is studied by nonequilibrium molecular dynamics (NEMD) and equilibrium molecular dynamics (EMD) with a high-shear-rate version of the nonequilibrium (NE) potential obtained recently from the NE distribution function theory of Gan and Eu [Phys. Rev. A 45, 3670; 46, 6344 (1992)]. The theory suggests a NE potential under which the equilibrium structure of the fluid is that of a NE fluid, and also suggests a corresponding Ornstein-Zernike equation with its closure relations. As in the low-shear-rate case [Yu. V. Kalyuzhnyi, S. T. Cui, P. T. Cummings, and H. D. Cochran, Phys. Rev. E 60, 1716 (1999)] the agreement between EMD and the modified hypernetted chain version of the theory is good. Although the high-shear-rate version of the NE potential improves the agreement between NEMD and EMD results (in comparison with the low-shear-rate version), its predictions are still unsatisfactory. With the high-shear-rate NE potential, EMD gives qualitatively correct predictions only for the shift of the position of the first maximum of the NE distribution function. The corresponding changes in the magnitude of the first maximum predicted by EMD have an opposite direction in comparison with those predicted by NEMD. It is concluded that the NE potential used is not very successful, and more accurate models for the potential are needed.

Anisotropic pair distribution functions for a simple, soft sphere fluid at moderate and high density under shear have been calculated by nonequilibrium molecular dynamics, by equilibrium molecular dynamics with a nonequilibrium potential, and by a nonequilibrium distribution function theory [H. H. Gan and B. C. Eu, Phys. Rev. A 45, 3670 (1992)] and some variants. The nonequilibrium distribution function theory consists of a nonequilibrium Ornstein-Zernike relation, a closure relation, and a nonequilibrium potential and is solved in spherical harmonics. The distortion of the fluid structure due to shear is presented as the difference between the nonequilibrium and equilibrium pair distribution functions. From comparison of the results of theory against results of equilibrium molecular dynamics with the nonequilibrium potential at low shear rates, it is concluded that, for a given nonequilibrium potential, the theory is reasonably accurate, especially with the modified hypernetted chain closure. The equilibrium molecular-dynamics results with the nonequilibrium potential are also compared against the results of nonequilibrium molecular dynamics and suggest that the nonequilibrium potential used is not very accurate. In continuing work, a nonequilibrium potential better suited to high shear rates [H. H. Gan and B. C. Eu, Phys. Rev. A 46, 6344 (1992)] is being tested.