Structure of a tractable stochastic mimic of soft particles

Abstract

The structure and assembly of soft particles is difficult to characterize because their interpenetrability allows them to be packed at ever higher density albeit with an increasing penalty in energy and/or pressure. Alternatively, the use of impenetrable particles (such as hard spheres) as a reference model for soft particles can fail because the packing densities are limited by the impossibility of complete space filling. We recently introduced the stochastic penetration algorithm (SPA) so as to allow for the computationally efficient integration of hard sphere models while including overlaps seen in soft interactions [Craven et al., J. Chem. Phys., 2013, 138, 244901]. Moving beyond the initial one-dimensional case studied earlier, we now consider the spatial properties of systems of stochastically penetrable spheres in dimensions d ≤ 3 through the use of molecular dynamics simulations and analytic methods. The stochastic potential allows spheres to either interpenetrate with a probability δ or collide elastically otherwise. For δ > 0 the particles interpenetrate (overlap), reducing the effective volume occupied by the particles in the system. We find that the occupied volume can be accurately predicted using analytic expressions derived from mean field arguments for the particle overlap probabilities with the exception of an observed clustering regime. This anomalous clustering behavior occurs at high densities and small δ. We find that this regime is coincident with that observed in deterministic penetrable models. The behavior of the stochastic penetrable particles also indicates that soft particles would be characterizable through a single reduced parameter that captures their overlap probability.