Structural relaxation of polydisperse hard spheres: comparison of the mode-coupling theory to a Langevin dynamics simulation

TL;DR

This study compares mode-coupling theory predictions with Brownian dynamics simulations for polydisperse hard spheres, revealing good agreement in collective dynamics but notable discrepancies in tagged-particle behavior at small wave numbers.

Contribution

It provides a detailed comparison of MCT with simulations for polydisperse systems, highlighting the importance of polydispersity and the limitations of MCT in describing self-diffusion.

Findings

Good agreement of collective dynamics with MCT when polydispersity is included.

Discrepancies in tagged-particle dynamics at small wave numbers.

Deviations from MCT near the glass transition in self-diffusion.

Abstract

We analyze the slow, glassy structural relaxation as measured through collective and tagged-particle density correlation functions obtained from Brownian dynamics simulations for a polydisperse system of quasi-hard spheres in the framework of the mode-coupling theory of the glass transition (MCT). Asymptotic analyses show good agreement for the collective dynamics when polydispersity effects are taken into account in a multi-component calculation, but qualitative disagreement at small $q$ when the system is treated as effectively monodisperse. The origin of the different small-$q$ behaviour is attributed to the interplay between interdiffusion processes and structural relaxation. Numerical solutions of the MCT equations are obtained taking properly binned partial static structure factors from the simulations as input. Accounting for a shift in the critical density, the collective density correlation functions are well described by the theory at all densities investigated in the simulations, with quantitative agreement best around the maxima of the static structure factor, and worst around its minima. A parameter-free comparison of the tagged-particle dynamics however reveals large quantiative errors for small wave numbers that are connected to the well-known decoupling of self-diffusion from structural relaxation and to dynamical heterogeneities. While deviations from MCT behaviour are clearly seen in the tagged-particle quantities for densities close to and on the liquid side of the MCT glass transition, no such deviations are seen in the collective dynamics.