Orientational structure of dipolar hard spheres near a hard neutral wall

Spherical boundaries are used in a Monte Carlo simulation to calculate the angular structure of dipolar hard spheres near a neutral hard wall.     

On the thermodynamics of hard spheres near a soft repulsive wall

We extend the variational method based on the Gibbs-Bogolioubov inequality to the case of fluids against a wall. We investigate the influence of the softness of the wall on the free energy of the system. For small packing fraction we consider a density expansion. The variational results are compared with the exact ones which are given by a direct expansion of the free energy. A comparison between variational and perturbation methods has been done for small packing fraction and also for a case corresponding to the liquid state. The accuracy of the present extension of the variational method to a surface phenomena is found as good as in the bulk fluid. A very simple expression is given for the change on surface tension when we go from the perfect hard wall to soft repulsive wall.     

A comprehensive approach to an equation of state for hard spheres and Lennard-Jones fluids

We present a simple method of obtaining various equations of state for hard sphere fluid in a simple unifying way.We will guess equations of state by using suitable axiomatic functional forms (n=1,2,3,4,5) for surface tension S n m (r),r ≥ d/2 with intermolecular separation r as a variable,where m is an arbitrary real number (pole).Among the equations of state obtained in this way are Percus-Yevick,scaled particle theory and Carnahan-Starling equations of state.In addition,we have found a simple equation of state for the hard sphere fluid in the region that represents the simulation data accurately.It is found that for both hard sphere fluids as well as Lennard-Jones fluids,with m=3/4 the derived equation of state (EOS) gives results which are in good agreement with computer simulation results.Furthermore,this equation of state gives the Percus-Yevick (pressure) EOS for the m=0,the Carnahan-Starling EOS for m=4/5,while for the value of m=1 it corresponds to a scaled particle theory EOS.     

Solution of the Ornstein-Zernike equation for a mixture of hard ions and Yukawa closure

The solution of the Ornstein-Zernike equation with Yukawa closure discussed in an earlier paper is simplified and extended to the more general case of several exponentials with real or complex exponents. The interesting case of an ionic mixture with Yukawa closure is solved explicitly. This case corresponds to ionic melts (molten salts).Supported by the Center of Environment and Energy Research of the University of Puerto Rico, OCEGI, and in part by NSF grant CHE-77-14611.     

A note on the Boltzmann equation for hard spheres

A simple form of the Boltzmann kinetic equation for hard spheres is proposed.     

Density fluctuations and the structure of a nonuniform hard sphere fluid

We derive an exact equation for density changes induced by a general external field that corrects the hydrostatic approximation where the local value of the field is adsorbed into a modified chemical potential. Using linear response theory to relate density changes self-consistently in different regions of space, we arrive at an integral equation for a hard sphere fluid that is exact in the limit of a slowly varying field or at low density and reduces to the accurate Percus-Yevick equation for a hard core field. This and related equations give accurate results for a wide variety of fields.     

Orientational structure in a monolayer of dipolar hard spheres

Off-lattice Monte Carlo simulations have been employed to investigate the orientational structure in a quasi-2-dimensional system of dipolar hard spheres covering both the fluid and crystal regions. The study includes pattern formation resulting from the competition of the long range dipolar interaction with localized interactions typical of those encountered in thin magnetic films.     

The effective interactions between colloidal hard spheres in microporous media: Hypernetted chain approximation for replica Ornstein-Zernike equations

In this work, the effective interaction between hard sphere colloidal particles in the presence of a hard sphere solvent, both dispersed either in a disordered quenched matrix of hard spheres or in the random matrix of freely overlapping obstacles is analyzed, using the replica Ornstein-Zernike (ROZ) integral equations. The ROZ equations are supplemented by the hypernetted chain closure. The presence of either disordered or random matrix is manifested in the attractive minima of the colloid-colloid potential of mean force (PMF), in addition to a set of minima due to the presence of solvent species. The effects of matrix microporosity and solvent density on the PMF and the intercolloidal forces are investigated. This project has been supported in part by the National Council for Science and Technology of Mexico (CONACyT) under Grant 25301-E.     

The Ornstein-Zernike equation for a fluid in contact with a surface

(Molecular Physics, 1976, 31, 1291)     

Solution of the Ornstein-Zernike equation for a soft-core Yukawa fluid

A model for simple fluids is proposed in which the radial distribution function has a parametric form appropriate to a soft-core fluid for interparticle separationr R, whereR is some range parameter. Forr > R, the direct correlation function is assumed to be of Yukawa form. The Ornstein-Zernike equation is solved for this system, yielding the radial distribution and the total correlation function for the entire range of interparticle separation. Methods of relating the model fluid to a real fluid by assigning values to the parameters are discussed.Supported by ARGC grant No. B7715646R.     

Analytic solution of Percus-Yevick equation for fluid of hard spheres

A new method of analytic solution of the Percus-Yevick equation for the radial distribution functiong(r) of hard-sphere fluid is proposed. The original non-linear integral equation is reduced to non-homogeneous linear integral equation of Volterra's type of the second order. The kernel of this new equation has a polynomial form which allows to find analytic expression forg(r) itself without using the Laplace transformation. In addition, the first three moments of the total correlation function can be found.     

Adsorption of dipolar hard spheres onto a smooth,hard wall in the presence of an electric field

Integral equations have been solved for the density profile of dipolar hard spheres against a hard, smooth wall in the presence of an electric field. This density profile was examined as a function of the bulk medium's temperature and density with different field strengths and field directions. It was found to depend primarily upon the competitive interactions of the field with the monolayer particles and the first outer shell with the monolayer particles.Supported by the ARGC.     

Solution of the Ornstein-Zernike equation with Yukawa closure for a mixture

The Ornstein-Zernike equation with Yukawa closure forr > _ij] for a mixture is solved. We utilize the Fourier transform or factorization technique introduced by Baxter. The general solution is obtained in the form of algebraic equations.     

The density profile for the Klein-Kramers equation near an absorbing wall

We derive asymptotic series for the expansion coefficients of a function in terms of the Pagani functions, which occur in the boundary layer solutions of the Klein-Kramers equation. The results enable us to determine the density profile in the stationary solution of this equation near an absorbing wall from the numerically determined velocity distribution at the wall, with an accuracy of about 2%. We also obtain information about the analytic behavior of the density profile: this profile increases near the wall with the square root of the distance to the wall. Finally, the asymptotic analysis leads to an understanding of the slow convergence of variational approximations to the solution of the absorbing-wall problem and of the exponents that occur when one studies the variational approximations to various quantities of interest as functions of the number of terms in the variational ansatz. This is used to obtain a better variational estimate for the density at the wall.     

Integral equation approximations for fluids of hard spheres with linear quadrupoles

In this paper we solve numerically several integral equation theories for the dense quadrupolar hard-sphere fluid. Closure approximations obtained by expanding the hypernetted-chain equation are shown to give pair-correlation functions and internal energies in good agreement with Monte Carlo calculations. The mean spherical approximation, however, is found to be extremely poor.     

Solution of the Yukawa closure of the Ornstein-Zernike equation

The solution of the Ornstein-Zernike equation with Yukawa closure [c(r)= forr>1] is generalized for an arbitrary number of Yukawas, using the Fourier transform technique introduced by Baxter. Full equivalence to the results of Waisman, Høye, and Stell is proved for the case of a single Yukawa. Finally, a convenient form of the Laplace transform ofg(s) is found, which can be easily inverted to give a stepwise, rapidly converging series forg(r).This research was partially supported by National Science Foundation, the Norwegian Research Council for Science and Humanities, and the donors of the Petroleum Research Fund, administered by the American Chemical Society.     

Approximate solution of the Percus-Yevick equation for a binary mixture of hard spheres with non-additive diameters

We present an approximate solution of the Percus-Yevick integral equation for a binary mixture of hard spheres with non-additive diameters. Defining R_ij the distance of closest approach between particles of species i and j by R ₁₂ = ½(R ₁₁ + R ₂₂) + α, we obtain a closed set of equations for the direct correlation functions c_ij (r) when 0 < α ? min [½(R ₂₂ - R ₁₁), ½R ₁₁]. Our expressions for c_ii (r), and for c ₁₂(r) in the range 0 < r ? ½[R ₂₂ - R ₁₁] - α, agree with those previously obtained by Lebowitz and Zomick.