Triggering Gaussian-to-Exponential Transition of Displacement Distribution in Polymer Nanocomposites <i>via</i> Adsorption-Induced Trapping

Abstract

In many disordered systems, the diffusion of classical particles is described by a displacement distribution P ( x, t ) that displays exponential tails instead of Gaussian statistics expected for Brownian motion. However, the experimental demonstration of control of this behavior by increasing the disorder strength has remained challenging. In this work, we explore the Gaussian-to-exponential transition by using diffusion of poly(ethylene glycol) (PEG) in attractive nanoparticle–polymer mixtures and controlling the volume fraction of the nanoparticles. In this work, we find “knobs”, namely nanoparticle concentration and interaction, which enable the change in the shape of P ( x, t ) in a well-defined way. The Gaussian-to-exponential transition is consistent with a modified large deviation approach for a continuous time random walk and also with Monte Carlo simulations involving a microscopic model of polymer trapping via reversible adsorption to the nanoparticle surface. Our work bears significance in unraveling the fundamental physics behind the exponential decay of the displacement distribution at the tails, which is commonly observed in soft materials and nanomaterials.