SAFT-D theory for hard sphere and hard disc chain fluids

SAFT-dimer (SAFT-D) theory is reformulated to yield an improved equation of state for the hard sphere chain fluid. Two sets of the equation of state are proposed by employing Chiew's expressions for the contact values of the m hard sphere site-site correlation function g(σ). Comparison with molecular simulation data shows that the improved SAFT-D equation of state predicts the compressibility factor more accurately than Ghonasgi and Chapman's equation of state. It has been shown that SAFT-dimer theory can be applied readily to fused hard sphere chain fluids by considering the correct value of the effective chain length (m*). SAFT-dimer theory is also extended to the 2-dimensional tangent and fused hard disc chain fluids. For the fused hard disc dimer fluid, the SAFT equation of state is found to be more accurate than the Boublik hard disc dimer equation of state. For tangent hard disc chain fluids, the results obtained from SAFT-dimer theory are compared with Monte Carlo results for 5-mers and with GFD theory for 4-mers, 8-mers and 16-mers.     

Extended hydrodynamic modes in a dense hard sphere fluid

A computer simulation experiment of a dense hard sphere fluid of 256 particles shows that the intermediate scattering function and the longitudinal velocity correlation function can be described by three extended hydrodynamic modes, the properties of which agree well with those predicted by the revised Enskog theory.     

Dense and nearly jammed random packings of freely jointed chains of tangent hard spheres

Dense packings of freely jointed chains of tangent hard spheres are produced by a novel Monte Carlo method. Within statistical uncertainty, chains reach a maximally random jammed (MRJ) state at the same volume fraction as packings of single hard spheres. A structural analysis shows that as the MRJ state is approached (i) the radial distribution function for chains remains distinct from but approaches that of single hard sphere packings quite closely, (ii) chains undergo progressive collapse, and (iii) a small but increasing fraction of sites possess highly ordered first coordination shells.     

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.     

Thermodynamic properties and phase equilibria of charged hard sphere chain model for polyelectrolyte solutions

A recent thermodynamic perturbation theory for flexible polyelectrolyte solutions is extended to study thermodynamic properties and phase equilibria for polyelectrolyte solutions with different polyion, chain lengths. Osmotic pressure, activity coefficient of an individual ion (polyion or counterion) and average activity coefficient are calculated. Except for the activity coefficient of the polyion, the chain length dependence of the properties is small. Also presented are vapour-liquid equilibrium coexisting curves, vapour pressures and critical points. As the polyion chain length approaches infinity the critical properties (temperature, pressure and density) become constants.     

The pressure of a hard sphere fluid on a curved surface

Utilizing the integral equation approach to the hard sphere fluid system developed in the preceding paper, the hard sphere-hard wall interaction is studied. For the case of a flat wall, perturbation solutions of the integral equation valid to second and third order in the packing fraction,y, are derived. For a surface of arbitrary curvature, an equation of state valid to second order in the packing fraction is also derived. When applied to very small cavities, it is found that the pressure at high densities is significantly higher than it would be for a flat wall.     

The adsorption of a hard sphere fluid in a slit-like pore filled with a disordered matrix of hard spheres: attractive wall-hard sphere interaction

The adsorption of a hard sphere fluid in a slit-like pore filled with a disordered hard sphere matrix is studied using the inhomogeneous Ornstein-Zernike equation with hypernetted chain closure. In contrast to previous studies, an attractive wall-hard sphere interaction is considered. The adsorption is affected by the attractive interaction both directly by the fluid-wall interaction and indirectly by the change in the structure of the matrix. Density profiles and pair distribution functions are reported. For comparison, grand canonical Monte Carlo simulation data are obtained. The agreement of the theoretical and simulation results is satisfactory but somewhat less pleasing than for the purely repulsive case.     

Evaluating virial coefficients for multicomponent mixtures: hard sphere mixtures and flexible chains

A new algorithm to compute the virial coefficients of multicomponent mixtures is proposed. The number of graphs that must be evaluated increases dramatically in a multicomponent mixture so that it becomes difficult to enumerate and compute all possible graphs. However, once all of them are known and evaluated, the virial coefficient of the mixture can be evaluated for any composition. If one is interested in the virial coefficient of a mixture of a certain composition, then a simpler approach can be followed. Starting from the graphs of a pure fluid, we assign a random chemical identity to each of the molecules of the graph. The probability of assigning a given chemical identity is taken from the composition of the mixture. In this way composition is treated as a random variable within the Monte Carlo procedure which determines the virial coefficient. The algorithm is checked by comparison with the virial coefficients of binary hard spheres mixtures which are well known. Good agreement is found. The procedure is then extended to multicomponent mixtures of hard spheres. Finally the procedure is applied to the determination of the virial coefficients of a flexible molecule. For flexible molecules the possible configurations of the molecules are treated as different components of the mixture. In this way we present what appears to be the first determination of the third and fourth virial coefficients of polymers in the continuum.     

Analytical expressions for the correlation function of a hard sphere dimer fluid

A closed form expression is given for the correlation function of a hard sphere dimer fluid. A set of integral equations is obtained from Wertheim's multidensity Ornstein-Zernike integral equation theory with Percus-Yevick approximation. Applying the Laplace transformation method to the integral equations and then solving the resulting equations algebraically, the Laplace transforms of the individual correlation functions are obtained. By the inverse Laplace transformation, the radial distribution function (RDF) is obtained in closed form out to 3D (D is the segment diameter). The analytical expression for the RDF of the hard dimer should be useful in developing the perturbation theory of dimer fluids.     

The second dielectric virial coefficient of a dipolar sticky hard sphere fluid

We calculate the second dielectric virial coefficient, B _?, of a fluid whose molecules are sticky hard spheres with embedded central point dipoles. The effect of stickiness is to increases B _? markedly.     

球在可自由移动的球形空腔内作纯滚动的运动分析

对在光滑水平面上可自由移动的球形空腔内作纯滚动的球的运动进行分析,给出球心及其边缘上任意一点在静止参考系中的运动轨迹方程,并绘出它们相应的轨迹,求出球在球形空腔内平衡位置附近作小振动的周期,并和球在可自由移动的球形空腔内作纯滑动的情况作了比较.     

First quantum correction to the radial distribution function and to the thermodynamic properties for a fluid of hard spheres

Dealing with the positions and orientations of the molecules as independent stochastic processes, the authors investigate the influence of translational and rotational fluctuations of anisotropically polarizable microsystems on the evolution in time of the second-order intensity correlation tensor of Rayleigh scattered light as well as on its spectral density. The notion of second-order depolarization is introduced and is shown to be a useful quantity for obtaining information on the translational and rotational motions of microsystems and their optical anisotropy.     

A new integral equation for the radial distribution function of a hard sphere fluid

Based on a proposal by Shinomoto, a new integral equation is derived for the radial distribution function of a hard-sphere fluid using mainly geometric arguments. This integral equation is solved by a perturbation expansion in the density of the fluid, and the results obtained are compared with those from molecular dynamics simulations and from the Born-Green-Yvon (BGY) and Percus-Yevick (PY) theories. The present theory provides results for the radial distribution function which are intermediate in accuracy between those obtained from the BGY and from the PY theories.     

The orientational pair correlation functions in a dense hard sphere fluid at long times

The two-particle contribution to the potential part of the stress tensor autocorrelation function of a dense hard sphere fluid is studied. It is shown that the long-time decay is given as the solution of a diffusion equation for the relative particle in a potential of mean force. The diffusion constant needed in order to accurately reproduce molecular dynamics results is found to be somewhat lower than the self-diffusion constant.     

Dynamics of a hard sphere granular impurity

An impurity particle coupling to its host fluid via inelastic hard sphere collisions is considered. It is shown that the exact equation for its distribution function can be mapped onto that for an impurity with elastic collisions and an effective mass. The application of this result to the Enskog-Lorentz kinetic equation leads to several conclusions: (1) every solution in the elastic case is equivalent to a class of solutions in the granular case; (2) for an equilibrium host fluid the granular impurity approaches equilibrium at a different temperature, with a dominant diffusive mode at long times; (3) for a granular host fluid in its scaling state, the granular impurity approaches the corresponding scaling solution.     

Statistical geometry of hard sphere systems: exact relations for first-order phase transitions in multicomponent systems

Statistical geometry provides exact relations between the thermophysical properties of hard sphere systems and various geometric quantities. Utilizing recently derived relations that describe multicomponent hard sphere systems, we derive two new expressions which place rigorous constraints on the behaviour of geometric quantities across a first-order phase transition. Some implications of these constraints for a binary mixture of additive hard spheres are discussed.     

Thermodynamic properties of hard ellipsoid square-well fluid

The perturbation theory with non-spherical reference system is used for molecular fluid with angle-dependent square-well type potential. Simple analytic expressions are given for the thermodynamic properties such as the equation of state, excess free energy per particle, internal energy and internal heat capacity. The effects of anisotropy on the thermodynamic properties are discussed. The anisotropy effects increase with increase of density and decrease of temperature and depends on the anisotropy parameterx ₀.     

Density expansion of the radial distribution and bridge functions of the hard sphere fluid

The bridge function and the background correlation function (and consequently the radial distribution function) of the pure hard sphere fluid are expanded up to the sixth power in density. The calculations are based on the Ree–Hoover representation of the diagrams and Monte Carlo integration. The coefficients as functions of the particle–particle separation are fitted to splines taking into account discontinuities in higher derivatives up to the term of the order of (r- const)⁵.