Determination of viscoelastic properties by analysis of probe-particle motion in molecular simulations.

We present a technique for the determination of viscoelastic properties of a medium by tracking the motion of an embedded probe particle by using molecular dynamics simulations. The approach involves the analysis of the simulated particle motion by continuum theory; it is shown to work in both passive and active modes. We demonstrate that, for passive rheology, an analysis based on the generalized Stokes-Einstein relationship is not adequate to obtain the values of the viscoelastic moduli over the frequency range studied. For both passive and active modes, it is necessary to account for the medium and particle inertia when analyzing the particle motion. For a polymer melt system consisting of short chains, the values calculated from the proposed approach are in good quantitative agreement with previous literature results that were obtained using completely different simulation approaches. The proposed particle rheology simulation technique is general and could provide insight into the characterization of the mechanical properties in biological systems, such as cellular environments and polymeric systems, such as thin films and nanocomposites that exhibit spatial variation in properties over the nanoscale.