Self-diffusion coefficients and shear viscosity of inverse power fluids: from hard- to soft-spheres

Abstract

Molecular dynamics computer simulation has been used to compute the self-diffusion coefficient, D, and shear viscosity, η_s, of soft-sphere fluids, in which the particles interact through the soft-sphere or inverse power pair potential, ϕ(r) = ε(σ/r)ⁿ, where n measures the steepness or stiffness of the potential, and ε and σ are a characteristic energy and distance, respectively. The simulations were carried out on monodisperse systems for a range of n values from the hard-sphere (n → ∞) limit down to n = 4, and up to densities in excess of the fluid–solid co-existence value. A new analytical procedure is proposed which reproduces the transport coefficients at high densities, and can be used to extrapolate the data to densities higher than accurately accessible by simulation or experiment, and tending to the glass transition. This formula, DX^c−1 ∝ A/X + B, where c is an adjustable parameter, and X is either the packing fraction or the pressure, is a development of one proposed by Dymond. In the expression, −A/B is the value of X at the ideal glass transition (i.e., where D and η_s⁻¹ → 0). Estimated values are presented for the packing fraction and the pressure at the glass transition for n values between the hard and soft particle limits. The above expression is also shown to reproduce the high density viscosity data of supercritical argon, krypton and nitrogen. Fits to the soft-sphere simulation transport coefficients close to solid–fluid co-existence are also made using the analytic form, ln(D) = α_XX, and n-dependence of the α_X is presented (X is either the packing fraction or the pressure).