Equilibrium Theory of Simple Liquids
TL;DR: The perturbation theory of liquids developed recently by Weeks, Chandler, and Andersen (WCA) is examined in detail: each assumption introduced by these authors is tested by comparison with "exact" computer results as discussed by the authors.
Abstract: The perturbation theory of liquids developed recently by Weeks, Chandler, and Andersen (WCA) is examined in detail: Each assumption introduced by these authors is tested by comparison with "exact" computer results. It is shown that the basic assumptions of WCA are justified. An improved expression for the radial distribution function of the hard-sphere gas enables us to correct for some further inconsistent assumptions of the WCA theory. We then succeed in giving simple analytical expressions for the thermodynamic functions of the Lennard-Jones fluid shown to be quite good at high density. We show that the remainder of the perturbation series, which converges slowly at lower density, can be evaluated with the help of the Percus-Yevick equation. We therefore possess a unified theory of liquids which is especially simple at high density. Finally we reexpress the original WCA theory in an analytical form.
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TL;DR: In this paper, a modified Benedict-Webb-Rubin (MBWR) equation of state for the Lennard-Jones (LJ) fluid is presented and compared with the simulation data of this work, and previously published Gibbs ensemble data.
Abstract: We review the existing simulation data and equations of state for the Lennard-Jones (LJ) fluid, and present new simulation results for both the cut and shifted and the full LJ potential. New parameters for the modified Benedict-Webb-Rubin (MBWR) equation of state used by Nicolas, Gubbins, Streett and Tildesley are presented. In contrast to previous equations, the new equation is accurate for calculations of vapour-liquid equilibria. The equation also accurately correlates pressures and internal energies from the triple point to about 4·5 times the critical temperature over the entire fluid range. An equation of state for the cut and shifted LJ fluid is presented and compared with the simulation data of this work, and previously published Gibbs ensemble data. The MBWR equation of state can be extended to mixtures via the van der Waals one-fluid theory mixing rules. Calculations for binary fluid mixtures are found to be accurate when compared with Gibbs ensemble simulations.
1,247 citations
TL;DR: In this article, the authors derived expressions for changes in the thermodynamic properties due to association in mixtures of molecules with multiple bonding sites, where the equations are written in terms of a hard-core reference whose pair distribution function is known.
Abstract: As a continuation of our work on spherical associating molecules, we have derived expressions for changes in the thermodynamic properties due to association in mixtures of molecules with multiple bonding sites. The equations are written in terms of a hard-core reference whose pair distribution function is known. In practise, the hard-sphere reference mixture is the easiest to use. A reference system of homonuclear chains is examined in order to account for asymmetries in molecular shape; chains are constructed by bonding equal-sized spheres together. An equation of state for hard-sphere chains is obtained which is in good agreement with recent simulation data. Expressions for mixtures of homonuclear chains of different sizes are also presented. The approach is extended to examine associating chain molecules with multiple bonding sites. The phase equilibria of non-associating chains, and of associating chains with one or two bonding sites are determined. In this study, the separate effects of molecular ass...
1,115 citations
TL;DR: In this article, the authors present a review of recently achieved progress in the field of soft condensed matter physics, and in particular on the study of the static properties of solutions or suspensions of colloidal particles.
1,056 citations
TL;DR: In this article, closed nonlinear equations are derived for a self-consistent treatment of density propagation, self-diffusion and current relaxation in a classical monatomic fluid, and a simplified model is analyzed in detail.
Abstract: Closed nonlinear equations are derived for a self-consistent treatment of density propagation, self-diffusion and current relaxation in a classical monatomic fluid. The solution for a hard-sphere model system brings out a phase transition to a glass at the packing fraction 0.516. Approaching the transition from the glass side the particle mean-square displacement increases to a finite value. A simplified model is analysed in detail. Approaching the transition from the liquid side the diffusivity is predicted to decrease to zero with a power law with exponent 1.76 which the authors find to agree well with some experimental data. The low-frequency density spectrum is found to consist of two contributions; one is an elastic line of the frozen structure on the glass side, which then decays to a narrow diffusion broadened quasielastic peak on the fluid side; the other part is described by a dynamical scaling law and it yields in particular a spectrum diverging at the glass point with certain exponents.
817 citations
01 Nov 2011
TL;DR: In this paper, the authors introduce colloid science and rheology, and present an overview of colloid physics and its applications in viscoelastic media. But they do not discuss the role of non-spherical particles.
Abstract: 1. Introduction to colloid science and rheology 2. Hydrodynamic effects 3. Brownian hard spheres 4. Stable colloidal suspensions 5. Non-spherical particles 6. Weakly flocculated suspensions 7. Thixotropy 8. Shear thickening 9. Rheometry of suspensions 10. Suspensions in viscoelastic media 11. Advanced topics.
792 citations