Revealing hidden medium-range order in silicate glass-formers using many-body correlation functions

TL;DR

This study uses advanced many-body correlation functions to uncover and characterize the medium-range order in silicate glass-formers, revealing structural transitions and correlations with macroscopic properties.

Contribution

It introduces a novel application of many-body correlation functions to analyze medium-range order in network glassformers, providing new insights into their structural and property relationships.

Findings

Na concentration increases local structuring and inhomogeneity.

Ring size distribution broadens with depolymerization.

Structural correlation lengths relate to fragility and elasticity.

Abstract

The medium range order (MRO) in amorphous systems has been linked to complex features such as the dynamic heterogeneity of supercooled liquids or the plastic deformation of glasses. However, the nature of the MRO in these materials has remained elusive, primarily due to the lack of methods capable of characterizing this order. Here, we leverage standard two-body structural correlators and advanced many-body correlation functions to probe numerically the MRO in prototypical network glassformers, i.e., silica and sodium silicates, systems that are of importance in natural as well as industrial settings. With increasing Na concentration, one finds that the local environment of Na becomes more structured and the spatial distribution of Na on intermediate length scales changes from blob-like to channel-like, indicating a growing inhomogeneity in the spatial Na arrangement. In parallel, we find that the Si-O network becomes increasingly depolymerized, resulting in a ring size distribution that broadens. The radius of gyration of the rings is well described by a power-law with an exponent around 0.75, indicating that the rings are progressively more crumbled with increasing size. Using a recently proposed four-point correlation function, we reveal that the relative orientation of the tetrahedra shows a transition at a distance around 4 Angstroms, a structural modification that is not seen in standard two-point correlation functions. Furthermore, we find that the length scale characterizing the MRO is non-monotonic as a function of temperature, caused by the competition between energetic and entropic terms. Finally, we demonstrate that the structural correlation lengths as obtained from the correlation functions that quantify the MRO are correlated with macroscopic observables such as the kinetic fragility of the liquids and the elastic properties of the glasses.