MC simulation results for a hard core model of carbon tetrachloride

Monte Carlo simulations on a hard tetrahedron fluid (hard core model of CCl₄) have been performed. The average site-site correlation functions, their generalized (1, 0, 0) spherical harmonic expansion coefficients, equation of state, and virial coefficients have been calculated and compared with theoretical methods currently available. The RISM equation is less accurate for the model studied than for simpler models considered so far. For the equation of state the best results are obtained from the Boublik-Nezbeda equation which agrees with the simulation results throughout the density range considered.     

Equation of state of planar hard dumbells

An extension of the hard disc equation of state to planar hard dumbells is proposed and the determination of the characteristic geometric measures of dumbells with the reduced length L* ? ?2 is discussed. The second and third virial coefficients following from the proposed equation of state are evaluated and compared with the exact Monte Carlo data. Compressibility factors for four different elongations are calculated and compared with pseudoexperimental data and with results of other methods.     

Equation of state of long chain molecules and rings

An equation of state for long chain molecules has been proposed using statistical associating fluid theory (SAFT). The formalism derived here is based on the assumption that the chain is formed by the pairs of trimers. The equations of state for 48-mers and 192-mers are formulated and compared with Monte Carlo results. The theory has been developed to treat hard sphere molecules with two attraction sites to form a ring molecule. The equations of state for trimer, hexamer and 12-mer ring molecules have been formulated. There is excellent agreement with available Monte Carlo results. Second virial coefficients of tangent chain molecules and ring molecules have been determined numerically and compared with simulation results.     

A simple effective pair potential for the molecular simulation of the thermodynamic properties of ammonia

A new optimized effective pair potential model is proposed, which is appropriate for the prediction of thermodynamic properties of fluid ammonia including vapour—liquid coexistence data. The phase behaviour is determined using a recently developed version of the Gibbs ensemble Monte Carlo method. Furthermore, liquid structure characteristics, the dielectric constant and supercritical properties are determined by Monte Carlo simulations in the isothermal—isobaric ensemble. The second virial coefficient of the pair potential model is calculated over a broad range of temperature. All properties are compared with experimental data or results of a multi-parameter equation of state for ammonia. The new model is found to yield coexistence properties and second virial coefficients in good agreement with experimental data and the results of the equation of state, respectively.     

Three Semi-empirical Analytic Expressions for the Radial Distribution Function of Hard Spheres

Three simple analytic expressions satisfying the limitation condition at low densities for the radial distribution function of hard spheres are developed in terms of a polynomial expansion of nonlinear base functions and the Carnahan--Starling equation of state. The simplicity and precision for these expressions are superior to the well-known Percus--Yevick expression. The coefficients contained in these expressions have been determined by fitting the Monte Carlo data for the first coordination shell, and by fitting both the Monte Carlo data and the numerical results of Percus-Yevick expression for the second coordination shell. One of the expressions has been applied to develop an analytic equation of state for the square-well fluid, and the numerical results are in good agreement with the computer simulation data.     

The structure of two-dimensional dimerizing fluids from Wertheim’s Ornstein-Zernike equation

A dimerizing fluid of hard discs is studied using two-dimensional (2D) Wertheim’s Ornstein-Zernike (WOZ) equation and associative Percus-Yevick (APY) closure. Dimerization takes place due to site-site associative interactions. The dependences of the association constant on disc density at different association energies are obtained. We calculate the compressibility and the virial equations of state (EOS) using the solution of the WOZ equation. Theoretical structure and thermodynamics is compared with Monte Carlo computer simulation data. Extension of our solution for polymerizing models is of special interest for the development of EOS for 2D chain fluids. This work was supported in part by Cray Research of Mexico under University Research and Development grant program and by KBN of Poland under the Grant No. 3T09A06210.     

The virial coefficients of hard hypersphere binary mixtures

The third, fourth and fifth virial coefficients of hard hypersphere binary mixtures with dimensionality d = 4, 5 have been calculated for size ratios R ≥ 0.1, R = ≡ σ₂₂/σ₁₁, where σ _ii is the diameter of component i. The composition independent partial virial coefficients have been evaluated by Monte Carlo integration of the corresponding Mayer modified star diagrams. The results are compared with the predictions of Santos, S., Yuste, S. B., and Lopez de Haro, M., 1999, Molec. Phys., 96, 1 of the equation of state of a multicomponent mixture of hard hyperspheres, and the good agreement gives strong support to the validity of that recipe.     

Is it possible to infer the equation of state of a mixture of hard discs from that of the one-component system?

Based on exact asymptotic properties of the composition-independent virial coefficients of a binary mixture of hard discs in the limits α = σ₂/σ₁ → 0, α → 1 and α → ∞, R. J. Wheatley (1998, Molec. Phys., 93, 965) has recently proposed an approximate interpolation equation for these coefficients. In this note, the equation of state equivalent to this interpolation is obtained, expressing the compressibility factor of the mixture in terms of that of the pure system. An extension to an arbitrary number of components is also given. The equation of state derived here is compared with another one recently proposed by following a different route (Santos, A., Yuste, S. B., and López de Haro, M., 1999, Molec. Phys., 96, 1) and with Monte Carlo simulation results. It is shown that the latter equation is more accurate than the former one, at least for not too disparate mixtures (0.7 < α < 1).     

Molecular dynamics calculations of the hard-sphere equation of state

The equation of state of the hard-sphere fluid is studied by a Monte Carlomolecular dynamics method for volumes ranging from 25V ₀ to 1.6V ₀ , whereV ₀ is the close-packed volume, and for system sizes from 108 to 4000 particles. TheN dependence of the equation of state is compared to the theoretical dependence given by Salsburg for theNPT ensemble, after correction for the ensemble difference, in order to obtain estimates for the thermodynamic limit. The observed values of the pressure are compared with both the [3/2] and the [2/3] Padé approximants to the virial series, using Kratky's value for the fifth virial coefficientB ₅ and choosingB ₆ andB ₇, to obtain a least-squares fit. The resulting values ofB ₆ andB ₇ lie within the uncertainties of the Ree-Hoover-Kratky Monte Carlo estimates for these virial coefficients. The values ofB ₈,B ₉, andB ₁₀ predicted by our optimal [3/2] approximant are also reported. Finally, the Monte Carlo-molecular dynamics equation of state is compared with a number of analytic expressions for the hard-sphere equation of state.Work supported by the Office of Basic Energy Sciences, U.S. Department of Energy.     

On the quantum corrections to the virial coefficients of the equation of state of a fluid

The first quantum correction to the virial coefficients of the equation of state of a fluid is derived in the presence of a weak three-body potential ?(i, j, k). Results for the third and fourth virial coefficients are given. Representing the potential energy of interaction of a pair and a triplet, by the Lennard-Jones (12-6) model and the triple dipole dispersion potential model of Axilrod and Teller, the first quantum correction to the third virial coefficient is calculated for many values of T*. The theoretical result is compared with the experimental data of helium.     

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.     

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.     

Monte Carlo Simulation of Hard Hyperspheres in Six,Seven and Eight Dimensions for Low to Moderate Densities

The pair correlation function of hard hyperspheres in six, seven and eight dimensions is obtained from Monte Carlo simulations. The value of the pair correlation function at contact is compared with the results from molecular dynamics calculations and a variety of theoretical approaches. Remarkably good agreement is found with the simple, closed-form equations of Y. Song, E. A. Mason and R. M. Stratt, J. Phys. Chem., 93:6916–6919 (1989). The Monte Carlo results for the equation of state are compared with the theoretical expressions of M. Baus and J. L. Colot, Phys. Rev. A, 36:3912 (1987), M. Luban and J. P. J. Michels, Phys. Rev A, 41:6796 (1990), and high order virial expansions. In addition, in seven dimensions, comparisons are made with the exact PY solution provided by M. Robles, M. L. de Haro and A. Santos, J. Chem. Phys., 120:9113 (2004). Very good agreement was observed between theory and computer simulation in all dimensions.     

An alternative formulation of the virial expansion for simple fluids

A new analytical formulation of the virial expansion for simple fluids is presented. Starting from the usual expression of the partition function of a set of identical molecules, a Fourier transformation is performed. Then a systematic procedure formally allowing the computation of the virial coefficients in the reciprocal space is presented; the coefficients are finally expressed as multiple integral expressions in the reciprocal space, and focus is on the simple case of hard sphere fluids. Finally, an approximate recursion relation is proposed that allows an estimation to be obtained of those coefficients without having to actually perform the integrations; a comparison of the results is made with the equation of state by Carnahan and Starling and with the recent numerical results by Clisby and Mc Coy.     

Radial Distribution Functions for Molecules in the Universal Equation of State Model for Gaseous/Fluid/Condensed Systems

Analytical expressions and a numerical method for calculation of distribution functions of hard spheres gij(r) based on inverting the Laplace transform for functions rgij(r) obtained from the Percus—Yevick equation are obtained. The method for calculation of radial distribution functions is applicable for any distances between hard spheres; it is verified by comparison of numerical results and Monte Carlo simulations. The application of the developed method for calculation of the radial distribution functions of metal atoms is demonstrated. Distribution functions are required to construct a universal theoretical model of equation of state capable of describing both dense multicomponent gas and condensed substances (liquid or solid phases) with high accuracy which is substantially faster than computer experiments (Monte Carlo and molecular dynamics methods).     

Electron wave packets: Quantum statistics in path integral representation

Fundamental relations between ensemble-averaged kinetic energy, pressure, and virial are obtained for quantum many-particle systems at finite temperatures. A path-integral method is developed for calculating kinetic energy for mixed (quantum-classical) systems. The method eliminates the problem of divergent variance. Path-integral Monte Carlo simulations are performed to validate the method as applied to single-electron and electron-pair wave packets, with exact treatment of exchange symmetry and spin states. Quantitative results are compared with corresponding characteristics calculated for point charges.     

An equation of state for hard convex body chains

The thermodynamic perturbation theory of hard sphere chains is generalized to derive an equation of state for hard convex body chains. The hard convex body chain equation of state contains two parameters that are related directly and rigorously to the geometry of the hard convex body. The compressibility factors and second virial coefficients of chains composed of prolate spherocylinders, oblate spherocylinders and doublecones are calculated and compared with hard sphere chain calculations. The comparison indicates that the nature of the hard convex body has a profound influence on the properties of the chain.     

RESEARCH NOTE A method for predicting the virial coefficients of hard linear homonuclear molecules

This paper proposes a simple method for predicting the virial coefficients, up to the fifth, for hard linear homonuclear molecules. The method uses the virial coefficients for hard spherocylinders and hard linear tangent spheres to obtain the virial coefficients of linear fused hard spheres. The results are in very good agreement with the known values for the latter kind of molecules. Thus the method is suitable for predictive purposes when virial coefficients are not known, which makes it useful for the derivation of certain equations of state.