Importance of many-body correlations in glass transition: an example from polydisperse hard spheres

Abstract

Most of the liquid-state theories, including glass-transition theories, are constructed on the basis of two-body density correlations. However, we have recently shown that many-body correlations, in particular bond orientational correlations, play a key role in both the glass transition and the crystallization transition. Here we show, with numerical simulations of supercooled polydisperse hard spheres systems, that the lengthscale associated with any two-point spatial correlation function does not increase toward the glass transition. A growing lengthscale is instead revealed by considering many-body correlation functions, such as correlators of orientational order, which follows the lengthscale of the dynamic heterogeneities. Despite the growing of crystal-like bond orientational order, we reveal that the stability against crystallization with increasing polydispersity is due to an increasing population of icosahedral arrangements of particles. Our results suggest that, for this type of systems, many-body correlations are a manifestation of the link between the vitrification and the crystallization phenomena. Whether a system is vitrified or crystallized can be controlled by the degree of frustration against crystallization, polydispersity in this case.Comment: To appear in J. Chem. Phys. for a special issue on the Glass Transitio