Entropic Effects of Interacting Particles Diffusing on Spherical Surfaces

Abstract

We present a molecular dynamics and theoretical study on the diffusion of interacting particles embedded on the surface of a sphere. By proposing five different interaction potentials among particles, we perform molecular dynamics simulations and calculate the mean square displacement (MSD) of tracer particles under a crowded regime of high surface density. Results for all the potentials show four different behaviors passing from ballistic and transitory at very short times, to sub-diffusive and saturation behaviors at intermediary and long times. Making use of irreversible thermodynamics theory, we also model the last two stages showing that the crowding induces a sub-diffusion process similar to that caused by particles trapped in cages, and that the saturation of the MSD is due to the existence of an entropic potential that limits the number of accessible states to the particles. By discussing the convenience of projecting the motions of the particles over a plane of observation, consistent with experimental capabilities, we compare the predictions of our theoretical model with the simulations showing that these stages are remarkably well described in qualitative and quantitative terms.