Molecular dynamics simulation study of self-diffusion for penetrable-sphere model fluids

Molecular dynamics simulations are carried out to investigate the diffusion behavior of penetrable-sphere model fluids characterized by a finite energy barrier ϵ. The self-diffusion coefficient is evaluated from the time-dependent velocity autocorrelation function and mean-square displacement. Detailed insights into the cluster formation for penetrable spheres are gained from the Enskog factor, the effective particle volume fraction, the mean free path, and the collision frequency for both the soft-type penetrable and the hard-type reflective collisions. The simulation data are compared to theoretical predictions from the Boltzmann kinetic equation and from a simple extension to finite ϵ of the Enskog prediction for impenetrable hard spheres (ϵ→∞). A reasonable agreement between theoretical and simulation results is found in the cases of ϵ∗ ≡ ϵ/k(B)T=0.2, 0.5, and 1.0. However, for dense systems (packing fraction ϕ>0.6) with a highly repulsive energy barrier (ϵ∗ = 3.0), a poorer agreement was observed due to metastable static effects of clustering formation and dynamic effects of correlated collision processes among these cluster-forming particles.