On the calculation of the potential of mean force between atomistic nanoparticles.

We study the potential of mean force (PMF) between atomistic silica and gold nanoparticles in the vacuum by using molecular dynamics simulations. Such an investigation is devised in order to fully characterize the effective interactions between atomistic nanoparticles, a crucial step to describe the PMF in high-density coarse-grained polymer nanocomposites. In our study, we first investigate the behavior of silica nanoparticles, considering cases corresponding to different particle sizes and assessing results against an analytic theory developed by Hamaker for a system of Lennard-Jones interacting particles (H.C. Hamaker, Physica A 4, 1058 (1937)). Once validated the procedure, we calculate effective interactions between gold nanoparticles, which are considered both bare and coated with polyethylene chains, in order to investigate the effects of the grafting density [Formula: see text] on the PMF. Upon performing atomistic molecular dynamics simulations, it turns out that silica nanoparticles experience similar interactions regardless of the particle size, the most remarkable difference being a peak in the PMF due to surface interactions, clearly apparent for the larger size. As for bare gold nanoparticles, they are slightly interacting, the strength of the effective force increasing for the coated cases. The profile of the resulting PMF resembles a Lennard-Jones potential for intermediate [Formula: see text], becoming progressively more repulsive for high [Formula: see text] and low interparticle separations.