Anisotropic pair correlations in binary and multicomponent hard-sphere mixtures in the vicinity of a hard wall: A combined density functional theory and simulation study

TL;DR

This study combines density functional theory and simulations to analyze anisotropic pair correlations in multicomponent hard-sphere mixtures near a wall, revealing detailed structural insights and the accuracy of theoretical predictions.

Contribution

It provides a comprehensive comparison of density functional theory predictions with Brownian dynamics simulations for multi-component mixtures near a wall, highlighting areas of agreement and deviation.

Findings

Excellent theory-simulation agreement for one-particle densities and correlation functions.

Better predictive accuracy for six-component mixtures due to suppressed crystallization.

Insights into structural modulations, ordering, and glassy dynamics near walls.

Abstract

The fundamental measure approach to classical density functional theory has been shown to be a powerful tool to predict various thermodynamic properties of hard-sphere systems. We employ this approach to determine not only one-particle densities but also two-particle correlations in binary and six-component mixtures of hard spheres in the vicinity of a hard wall. The broken isotropy enables us to carefully test a large variety of theoretically predicted two-particle features by quantitatively comparing them to the results of Brownian dynamics simulations. Specifically, we determine and compare the one-particle density, the total correlation functions, their contact values, and the force distributions acting on a particle. For this purpose, we follow the compressibility route and theoretically calculate the direct correlation functions by taking functional derivatives. We usually observe an excellent agreement between theory and simulations, except for small deviations in cases where local crystal-like order sets in. Our results set the course for further investigations on the consistency of functionals as well as for structural analysis on, e.g., the primitive model. In addition, we demonstrate that due to the suppression of local crystallization, the predictions of six-component mixtures are better than those in bidisperse or monodisperse systems. Finally, we are confident that our results of the structural modulations induced by the wall lead to a deeper understanding of ordering in anisotropic systems in general, the onset of heterogeneous crystallization, caging effects, and glassy dynamics close to a wall, as well as structural properties in systems with confinement.