title: Thermodynamic properties and entropy scaling law for diffusivity in soft spheres.
abstract: The purely repulsive soft-sphere system, where the interaction potential is inversely proportional to the pair separation raised to the power n, is considered. The Laplace transform technique is used to derive its thermodynamic properties in terms of the potential energy and its density derivative obtained from molecular dynamics simulations. The derived expressions provide an analytic framework with which to explore soft-sphere thermodynamics across the whole softness-density fluid domain. The trends in the isochoric and isobaric heat capacity, thermal expansion coefficient, isothermal and adiabatic bulk moduli, Grüneisen parameter, isothermal pressure, and the Joule-Thomson coefficient as a function of fluid density and potential softness are described using these formulas supplemented by the simulation-derived equation of state. At low densities a minimum in the isobaric heat capacity with density is found, which is a new feature for a purely repulsive pair interaction. The hard-sphere and n = 3 limits are obtained, and the low density limit specified analytically for any n is discussed. The softness dependence of calculated quantities indicates freezing criteria based on features of the radial distribution function or derived functions of it are not expected to be universal. A new and accurate formula linking the self-diffusion coefficient to the excess entropy for the entire fluid softness-density domain is proposed, which incorporates the kinetic theory solution for the low density limit and an entropy-dependent function in an exponential form. The thermodynamic properties (or their derivatives), structural quantities, and diffusion coefficient indicate that three regions specified by a convex, concave, and intermediate density dependence can be expected as a function of n, with a narrow transition region within the range 5 < n < 8.
authors.affiliation: Institute of Molecular Physics, Polish Academy of Sciences, Mariana Smoluchowskiego 17, 60-179 Poznań, Poland.
authors.forename: S
authors.initials: S
authors.lastname: Pieprzyk
authors.affiliation: Department of Physics, Royal Holloway, University of London, Egham, Surrey TW20 0EX, United Kingdom.
authors.forename: D M
authors.initials: DM
authors.lastname: Heyes
authors.affiliation: Institute of Molecular Physics, Polish Academy of Sciences, Mariana Smoluchowskiego 17, 60-179 Poznań, Poland.
authors.forename: A C
authors.initials: AC
authors.lastname: Brańka
mesh_terms: D004058:Diffusion; D019277:Entropy; D006358:Hot Temperature; D056004:Molecular Dynamics Simulation