Dynamical facilitation governs glassy dynamics in suspensions of colloidal ellipsoids

One of the greatest challenges in contemporary condensed matter physics is to ascertain whether the formation of glasses from liquids is fundamentally thermodynamic or dynamic in origin. Although the thermodynamic paradigm has dominated theoretical research for decades, the purely kinetic perspective of the dynamical facilitation (DF) theory has attained prominence in recent times. In particular, recent experiments and simulations have highlighted the importance of facilitation using simple model systems composed of spherical particles. However, an overwhelming majority of liquids possess anisotropy in particle shape and interactions, and it is therefore imperative to examine facilitation in complex glass formers. Here, we apply the DF theory to systems with orientational degrees of freedom as well as anisotropic attractive interactions. By analyzing data from experiments on colloidal ellipsoids, we show that facilitation plays a pivotal role in translational as well as orientational relaxation. Furthermore, we demonstrate that the introduction of attractive interactions leads to spatial decoupling of translational and rotational facilitation, which subsequently results in the decoupling of dynamical heterogeneities. Most strikingly, the DF theory can predict the existence of reentrant glass transitions based on the statistics of localized dynamical events, called excitations, whose duration is substantially smaller than the structural relaxation time. Our findings pave the way for systematically testing the DF approach in complex glass formers and also establish the significance of facilitation in governing structural relaxation in supercooled liquids.The transformation of liquids into glasses is as ubiquitous as it is enigmatic. From the formation of obsidian during volcanic eruptions (1) and fabrication of superstrong metallic glasses (2) to exotic forms of slow dynamics in crystals of colloidal dimers (3) and Janus particles (4), glass formation pervades nature, industry, and academia. A vast majority of molecular glass-forming materials exhibit anisotropy in shape and interparticle interactions, which often has a profound influence on their glassy dynamics. The rapidly expanding repertoire of chemists has made it possible to design colloidal particles of desired shape and interactions that can serve as realistic experimental analogs of these molecular liquids (5). By contrast, prominent theories like the Adam–Gibbs (6) theory, random first-order transition (RFOT) theory (7, 8), and the dynamical facilitation (DF) theory (9, 10) have been tested predominantly on spherical glass formers with isotropic interactions, which exhibit gross features of glassy dynamics, but fail to capture the nuances of vitrification in complex systems.The discovery of growing static (11–16) and dynamic (17–21) length scales appears to support the thermodynamic perspective of the Adam–Gibbs and RFOT theories. However, the growth in static length scales over the dynamical range accessible to numerical simulations is often minuscule and much smaller than the corresponding growth in dynamic length scales (21, 22). This renders any causal connection between growing static length scales and growing timescales doubtful (22). Moreover, recent simulations (23) and colloid experiments (24) have shown that growing dynamical correlations in the form of string-like cooperative motion emerge naturally within the purely kinetic approach of the DF theory. To compound matters further, facilitation is present even within the RFOT framework, albeit as a consequence of slow dynamics rather than a cause (25). Thus, although DF has been shown to exist (23, 24, 26–29), its relative importance as a mechanism of structural relaxation is still debated (30–32). The application of the DF approach to complex glass formers will therefore not only enhance our understanding of glass transitions in these systems, but also help ascertain the relevance of facilitation in governing structural relaxation.Here, we apply the DF theory to elucidate glass formation in suspensions of colloidal ellipsoids with repulsive as well as attractive interactions. The DF theory claims that structural relaxation in glass-forming liquids proceeds via a process known as dynamical facilitation, whereby localized mobile regions, termed excitations, mediate motion in neighboring regions in a manner that conserves mobility (9, 10). We first show that the notions of localized excitations and facilitated dynamics can be extended even to orientational relaxation. Next, we demonstrate that the spatial decoupling of dynamical heterogeneities (DHs) observed in colloid experiments stems from the spatial decoupling of rotational and translational facilitation. Most importantly, the DF theory can predict the existence of recently observed reentrant glass transitions (33) from the density dependence of the concentration of excitations. Our findings not only highlight the importance of facilitated dynamics in anisotropic glass formers but also reinforce the claim that, in the broader context of the glass transition, facilitation dominates structural relaxation.