Dynamic light-scattering measurements are reported for suspensions at concentrations in the vicinity of the glass transition. In a mixture of identically sized but optically different particles having hard-sphere-like interactions, we project out the incoherent ͑or self-͒ intermediate scattering functions by adjusting the refractive index of the suspending liquid until scattering from the structure is suppressed. Due to polydispersity, crystallization is sufficiently slow so that good estimates of ensemble-averaged quantities can be measured for the metastable fluid states. Crystallization of the suspensions is still exploited, however, to set the volume fraction scale in terms of effective hard spheres and to eliminate ͑coherent͒ scattering from the structure. The glasstransition volume fraction is identified by the value where large-scale particle motion ceases. The nonequilibrium nature of the glass state is evidenced by the dependence on the waiting time of the long time decay of the relaxation functions. The self-intermediate scattering functions show negligible deviation from Gaussian behavior up to the onset of large-scale diffusion in the fluid or the onset of waiting time effects in the glass.

Amorphous solids, or glasses, are distinguished from crystalline solids by their lack of long-range structural order. At the level of two-body structural correlations, glassformers show no qualitative change upon vitrifying from a supercooled liquid. Nonetheless the dynamical properties of a glass are so much slower that it appears to take on the properties of a solid. While many theories of the glass transition focus on dynamical quantities, a solid's resistance to flow is often viewed as a consequence of its structure. Here we address the viewpoint that this remains the case for a glass. Recent developments using higher-order measures show a clear emergence of structure upon dynamical arrest in a variety of glass formers and offer the tantalising hope of a structural mechanism for arrest. However a rigorous fundamental identification of such a causal link between structure and arrest remains elusive. We undertake a critical survey of this work in experiments, computer simulation and theory and discuss what might strengthen the link between structure and dynamical arrest. We move on to highlight the relationship between crystallisation and glass-forming ability made possible by this deeper understanding of the structure of the liquid state, and emphasize the potential to design materials with optimal glassforming and crystallisation ability, for applications such as phase-change memory. We then consider aspects of the phenomenology of glassy systems where structural measures have yet to make a large impact, such as polyamorphism (the existence of multiple liquid states), aging (the time-evolution of non-equilibrium materials below their glass transition) and the response of glassy materials to external fields such as shear.Comment: 70 page

We introduce a simulation technique for creating dense random packings of hard particles. The technique is particularly suited to handle particles of different shapes. Dense amorphous packings of spheres have been formed, which are consistent with the existing work on random sphere packings. Packings of spherocylinders have also been simulated out to the large aspect ratio of alpha=160.0. Our method packs randomly oriented spherocylinders to densities that reproduce experimental results on anisotropic powders and colloids very well. Interestingly, the highest packing density of phi=0.70 is achieved for very short spherocylinders rather than spheres. This suggests that slightly changing the shapes of the particles forming a hard sphere glass could cause it to melt. Comparisons between the equilibrium phase diagram for hard spherocylinders and the densest possible amorphous packings have interesting implications on the crystallization of spherocylinders as a function of aspect ratio.

Fluctuation theorems, which have been developed over the past 15 years, have resulted in fundamental breakthroughs in our understanding of how irreversibility emerges from reversible dynamics, and have provided new statistical mechanical relationships for free energy changes. They describe the statistical fluctuations in time-averaged properties of many-particle systems such as fluids driven to nonequilibrium states, and provide some of the very few analytical expressions that describe nonequilibrium states. Quantitative predictions on fluctuations in small systems that are monitored over short periods can also be made, and therefore the arXiv:0709.3888v2 [cond-mat.stat-mech]

We study the relationship between local structural ordering and dynamical heterogeneities in a model glass-forming liquid, the Wahnström mixture. A novel cluster-based approach is used to detect local energy minimum polyhedral clusters and local crystalline environments. A structure-specific time correlation function is then devised to determine their temporal stability. For our system, the lifetime correlation function for icosahedral clusters decays far slower than for those of similarly sized but topologically distinct clusters. Upon cooling, the icosahedra form domains of increasing size and their lifetime increases with the size of the domains. Furthermore, these long-lived domains lower the mobility of neighboring particles. These structured domains show correlations with the slow regions of the dynamical heterogeneities that form on cooling towards the glass transition. Although icosahedral clusters with a particular composition and arrangement of large and small particles are structural elements of the crystal, we find that most icosahedral clusters lack such order in composition and arrangement and thus local crystalline ordering makes only a limited contribution to this process. Finally, we characterize the spatial correlation of the domains of icosahedra by two structural correlation lengths and compare them with the four-point dynamic correlation length. All the length scales increase upon cooling, but in different ways.

We describe the topological cluster classification (TCC) algorithm. The TCC detects local structures with bond topologies similar to isolated clusters which minimise the potential energy for a number of monatomic and binary simple liquids with m ≤ 13 particles. We detail a modified Voronoi bond detection method that optimizes the cluster detection. The method to identify each cluster is outlined, and a test example of Lennard-Jones liquid and crystal phases is considered and critically examined.

The mechanism by which a liquid may become arrested, forming a glass or gel, is a long-standing problem of materials science. In particular, long-lived (energetically) locally favoured structures (LFSs), the geometry of which may prevent the system relaxing to its equilibrium state, have long been thought to play a key role in dynamical arrest. Here, we propose a definition of LFSs which we identify with a novel topological method and directly measure with experiments on a colloidal liquid-gel transition. The population of LFSs is a strong function of (effective) temperature in the ergodic liquid phase, rising sharply approaching dynamical arrest, and indeed forms a percolating network that becomes the 'arms' of the gel. Owing to the LFSs, the gel is unable to reach equilibrium, crystal-gas coexistence. Our results provide direct experimental observation of a link between local structure and dynamical arrest, and open a new perspective on a wide range of metastable materials.

We study the random packing of non-spherical particles by computer simulation to investigate the effect of particle shape and aspect ratio on packing density and microstructure. Packings of cut spheres (a spherical segment which is symmetric about the centre of the sphere) are simulated to assess the influence of a planar face on packing properties. It turns out that cut spheres, in common with spherocylinders and spheroids, pack more efficiently as the particle's aspect ratio is perturbed slightly from unity (the aspect ratio of a sphere) to reach a maximum density at an aspect ratio of approximately 1.25. Upon increasing the aspect ratio further the cut spheres pack less efficiently, until approximately an aspect ratio of 2, where the particles are found to form a columnar phase. The amount of ordering is sensitive to simulation parameters and for very thin disks the formation of long columns becomes frustrated, resulting in a nematic phase, in marked contrast to the behavior of long thin rods which always randomly pack into entangled isotropic networks. With respect to coordination numbers it appears that cut spheres always pack with significantly fewer contacts than required for isostatic packing.