The mean spherical model for charged hard spheres

The reduced mean electrostatic potential v(r) and the radial distribution functions gij(r) for a system of charged hard spheres of equal diameter are calculated from the solution of the mean spherical model equation given by Waisman and Lebowitz. An analytical solution is given for v(r) and the gij(r) are shown to be the sum of the Percus-Yevick uncharged hard-sphere distribution function and an electrostatic term. The correct qualitative behaviour of the mean potential is predicted at high concentrations but the radial distribution functions are only accurate for low valency electrolytes at high concentrations.     

Solution of the mean spherical approximation for hard ions and dipoles of arbitrary size

The general solution of the mean spherical approximation (MSA) for an arbitrary mixture of hard spherical ions and dipoles, in which the ions can be of different size, is found. This solution is given in terms of three parameters that are calculated by solving an algebraic equation. Two of these parameters are scaling parameters required to satisfy the general symmetry of the pair correlation functions, and are similar to the one introduced in the solution of the MSA for an ionic mixture in earlier work. For equal size and low ionic concentration, we get a rather explicit solution of the MSA, which is formally similar to the Waisman-Lebowitz solution of the restricted primitive model, but with a concentration-dependent dielectric constant.Supported in part through NSF grant 77-04597.     

Rescaled mean spherical approximation structure factor for an aqueous suspension of polystyrene spheres

Rescaled mean spherical approximation (RMSA) has been used to calculate the structure factor for the aqueous suspension of polystyrene macroions with the interaction potential taken according to Derjaguin and Landau (1941) and Verwey and Overbeek (1948) (DLVO) model. The effects of charge over the macroion and size on the surface potential and therefore, the structure factor have been studied. The breakdown of the DLVO potential with an excess charge over the macroion (⩾800e) has been reported. The oscillation in the first peak height of structure factor versus wave vector curve with size has been correlated with the Debye length.     

Computer simulation of cavity pair distribution functions of hard spheres in a hard slit pore

We describe efficient Monte Carlo computer simulation techniques to calculate conditional distribution functions for pairs of hard-sphere (HS) cavities in a hard slit pore of width L, n* (z ₁,z ₂,r), and use these as an efficient route to calculating the corresponding dimensionless excess chemical potentials μ ^e (z ₁,z ₂,r). z_i is the distance of an HS centre from a (specified) wall and r is the distance between the cavity centres. This is the first calculation of such functions, which are of interest in their own right and provide data for the testing of theories, in addition to providing data for a simple model for the infinite dilution behaviour of a polyatomic solute in a simple molecularly confined solvent. Results are presented for special cases for the cavity functions n* (z ₁,z ₂,r) which occur when the spheres are in the same plane, when the line of sphere centres is perpendicular to the walls, and when the spheres are in contact. We compare results obtained using the Kirkwood superposition approximation in conjunction with results obtained from the computer simulation data using the first member of the BGY integral equation hierarchy. The approximation is found to be exact in certain limiting geometrical situations, but in general is quantitatively poor.     

The mean spherical model for asymmetric electrolytes: thermodynamics and the pair correlation function

It is shown that the RISM theory of molecular liquids provides an accurate prediction of the measured neutron scattering structure factor of deuterated liquid chloroform.     

Glass transition line for the system of charged hard spheres

We locate the glass transition line of the charged-hard-sphere system in the density-temperature plane, using a mean-field hypernetted chain approximation within the replica-symmetry-breaking scenario [S. Franz and G. Parisi, Phys. Rev. Lett. 79 (1997) 2486. [11]]. Our results demonstrate a dominant role of the steric factor and explain the ineffectiveness of purely Coulombic interactions in driving phase transitions.     

Mean spherical model for hard ions and dipoles: Thermodynamics and correlation functions

The solution of the mean spherical model of a mixture of equal-size hard ions and dipoles is reinvestigated. Simple expressions for the coefficients of the Laplace transform of the pair correlation function and the other thermodynamic properties are given.Supported by DOE through the Center of Environment and Energy Research of the University of Puerto Rico and NSF Grant CH 77-14611.     

Relation between the free energy and the direct correlation function in the mean spherical approximation

It is shown that the direct correlation function of a mixture of hard ions in the mean spherical approximation (MSA) can be expressed in terms of overlap functions of charged spherical shells. In particular, if the system is a mixture of pairs of ions of equal size and opposite charge, then the MSA direct correlation function is given by the electrostatic energy of a pair of charged shells, of radius equal to the radius of the hard ion plus 1/(2). This direct correlation function can be derived from a free energy functional, and a simple extension to nonuniform systems is given.     

Modified equation of state for pure and hard sphere mixtures in mean ionic activity coefficient calculations by mean spherical approximation model

A hard sphere equation of state (EOS) based on tetrakaidecahedron cell geometry (instead of spherical shape) and highly optimized molecular dynamic simulation data is proposed. The EOS is extended to hard sphere mixture and its performance for compressibility factor calculation at different diameter size of hard sphere mixtures by using various mixing rule is compared with Monte Carlo simulation data. The results indicated that for all mixing rules, the proposed EOS has minimum error comparing with computer simulation data. Also the residual prosperities are derived by using the proposed EOS. The residual properties are used in mean spherical approximation model (MSA) to evaluate the mean ionic activity coefficient of aqueous electrolyte solutions. The results are compared with those obtained by similar hard sphere equations of state and it is shown that the proposed EOS has a better performance in predicting the mean ionic activity coefficient.     

Variational extension of the mean spherical approximation to arbitrary dimensions

We generalize a variational principle for the mean spherical approximation for a system of charged hard spheres in 3D to arbitrary dimensions. We first construct a free energy variational trial function from the Debye-Hückel excess charging internal energy at a finite concentration and an entropy obtained at the zero-concentration limit by thermodynamic integration. In three dimensions the minimization of this expression with respect to the screening parameter leads to the mean spherical approximation, usually obtained by solution of the Ornstein-Zernike equation. This procedure, which interpolates naturally between the zero concentration/coupling limit and the high-concentration/ coupling limit, is extended to arbitrary dimensions. We conjecture that this result is also equivalent to the MSA as originally defined, although a technical proof of this point is left for the future. The Onsager limitT ΔS ^MSA /ΔE ^MSA → 0 for infinite concentration/coupling is satisfied for all d ≠ 2, while ford=2 this limit is 1. On leave from Department of Physics, University of Puerto Rico, Mayagüez Campus, Mayagüez, Puerto Rico, 00681.     

Vapour-liquid equilibrium of the charged Yukawa fluid from Gibbs ensemble Monte Carlo simulations and the mean spherical approximation

A Gibbs ensemble Monte Carlo (GEMC) study supplemented by theoretical calculations using the mean spherical approximation (MSA) is reported for the charged Yukawa system. In this system the particles interact via an attractive Yukawa potential and a Coulomb potential. When the Coulomb potential is weak compared to the Yukawa attraction the results obtained for the vapour-liquid equilibrium from the GEMC and the MSA are very similar. On increasing the charge, the system becomes similar to the primitive model of electrolytes, and at high charges similar phenomena, such as ion association, are observed. At these charges, the MSA yields poorer results. Using both methods, an increase of the charge results in an increase of the critical temperature but a decrease of the critical density.     

On the freezing and structure of hard spheres under spherical confinement

The equation of state and the structure of hard spheres confined in spherical pores have been investigated via molecular dynamics for different pore radii ranging from 5.0 to 10.0?σ, where σ is the particle diameter. The hard boundary is chosen to capture the pure geometric effect of spherical confinement. A discontinuity in the equation of state was observed, indicating the onset of a freezing-like phase transition, which was similar to that of the bulk hard-sphere fluids. The behaviour of confined particles resembles that of the bulk with increase in the pore size, while its deviation from the bulk is found to be larger at the solid-like phase. For the pore radius below 5.0, FCC-like crystal clusters are not formed in spherically confined hard spheres.     

A solution of the multiple-binding mean spherical approximation for ionic mixtures

The mean spherical approximation (MSA) for an arbitrary mixture of charged hard spheres with saturating bonds is solved in the Wertheim formalism. Any number of bonds is allowed. It is shown that the general solution is given in terms of a screening MSA-like parameter ^T , a cross-interaction parameter that will depend on the binding association equations, the set of binding association fractions, and an additional algebraic equation. The equation for ^T is given for the general case. The equation for , however, depends strongly on the particular closure that is used to compute the contact pair correlation function. The full solution requires, as in the dimer case recently solved by Blum and Bernard, solvingm+2 equations and additionally the inversion of a matrix of size [(–1)m] for a system withm components and bonds. We recall that when =1, only dimers are allowed; for =2, only linear chains are formed: and when 3, branching of the polymers occurs. It can be shown that the excess entropy for the polymer case is as before,S ^MSA=( ^T )³/3 + sticky terms, where the sticky terms depend on the model and will be given in future work.     

The general solution of the binding mean spherical approximation for pairing ions

The mean spherical approximation (MSA) for an arbitrary mixture of charged hard spheres with saturating bonds is solved in the Wertheim formalism. Only pairs are allowed. It is shown that the general solution is given in terms of two scaling parameters and the set of binding fractions. One of the scales is the screening parameter, and the other is a coupling parameter analogous to that of the simple MSA, but that now is found solving a cubic equation. Therefore the full solution requires solvingm+2 nonlinear algebraic equations for a system withm components. A brief discussion of the thermodynamics is given.     

On the isothermal density derivative ofG(r) and a new theory of the pair correlation function of hard spheres

A new representation is obtained for the isothermal density derivative ofg(r). It explicitly exhibits the contributions of potential energy terms that are not pairwise additive. Consideration of a previously known result shows that one has to be rather cautious when using it to obtain information on the triplet correlation function from the well-known relation between this function andg/, due to large cancellations which take place at high density. By integrating with respect to density the new representation forg/, after a suitable closure has been introduced, we obtain an augmented Percus-Yevick equation for hard spheres which has full thermodynamic consistency. The equation of state and the cavity functiony(r) are very accurate at low density and considerably improve PY at medium density, so that this appears to be a useful new approach to the theory of fluids, but it is necessary to improve the closure in order to treat a dense fluid.This paper is dedicated to Jerry Percus on the occasion of his 65th birthday.     

Analytic solution of the mean spherical approximation for ion-dipole model in a neutralizing background

The analytic solution of the mean spherical approximation (MSA) for a multicomponent mixture of hard ions and hard dipoles with arbitrary valences and sizes of particles in a uniform neutralizing background is found. Expressions for the pair correlation functions and thermodynamics in the MSA are obtained.     

Critical parameters of asymmetric primitive model electrolytes in the mean spherical approximation

The effect of size and charge asymmetries on the critical parameters of primitive model electrolytes is comprehensively surveyed by using the mean spherical approximation.