The role of fivefold symmetry in suppressing crystallization

Although long assumed to have an important role in the suppression of crystallization and the development of glassformers, the effect of local fivefold symmetry has never been directly tested. Here we consider whether such suppression of crystallization has a kinetic or thermodynamic nature and investigate its mechanism. We introduce a model in which the degree of fivefold symmetry can be tuned by favouring arrangements of particles in pentagonal bipyramids. We thus show that fivefold symmetry has both kinetic and thermodynamic effects on the mechanism of crystallization to a face-centred cubic crystal. Our results suggest that the mechanism of crystallization suppression is related to the surface tension between fluid and crystal. Interestingly, the degree of fivefold symmetry has little effect on crystal growth rate, suggesting that growth may be only weakly coupled to fluid structure in hard sphere like systems. Upon increasing the fivefold symmetry, we find a first-order transition to an alternative icosahedra-rich phase. At intermediate bias strengths we find a one-component glassformer

A structural comparison of models of colloid-polymer mixtures

We study the structure of colloidal fluids with reference to colloid-polymer mixtures. We compare the one component description of the Asakura-Oosawa (AO) idealisation of colloid-polymer mixtures with the full two-component model. We also consider the Morse potential, a variable range interaction, for which the ground state clusters are known. Mapping the state points between these systems, we find that the pair structure of the full AO model is equally well described by the Morse potential or the one component AO approach. We employ a recently developed method to identify in the bulk fluid the ground state clusters relevant to the Morse potential. Surprisingly, when we measure the cluster populations, we find that the Morse fluid is significantly closer the full AO fluid than the one component AO description.Comment: 13 pages, accepted by J. Phys. Condens: Matter special issue for CECAM meeting 'New Trends in Simulating Colloids: from Models to Applications

The effect of attractions on the local structure of liquids and colloidal fluids

We revisit the role of attractions in liquids and apply these concepts to colloidal suspensions. Two means are used to investigate the structure; the pair correlation function and a recently developed topological method. The latter identifies structures topologically equivalent to ground state clusters formed by isolated groups of 5 < m < 13 particles, which are specific to the system under consideration. Our topological methodology shows that, in the case of Lennard-Jones, the addition of attractions increases the system's ability to form larger (m>8) clusters, although pair-correlation functions are almost identical. Conversely, in the case of short-ranged attractions, pair correlation functions show a significant response to adding attraction, while the liquid structure exhibits a strong decrease in clustering upon adding attractions. Finally, a compressed, weakly interacting system shows a similar pair structure and topology.Comment: 22 page

Structure and kinetics in the freezing of nearly hard spheres

We consider homogeneous crystallisation rates in confocal microscopy experiments on colloidal nearly hard spheres at the single particle level. These we compare with Brownian dynamics simuations by carefully modelling the softness in the interactions with a Yukawa potential, which takes account of the electrostatic charges present in the experimental system. Both structure and dynamics of the colloidal fluid are very well matched between experiment and simulation, so we have confidence that the system simulated is close to that in the experiment. In the regimes we can access, we find reasonable agreement in crystallisation rates between experiment and simulations, noting that the larger system size in experiments enables the formation of critical nuclei and hence crystallisation at lower supersaturations than the simulations. We further examine the structure of the metastable fluid with a novel structural analysis, the topological cluster classification. We find that at densities where the hard sphere fluid becomes metastable, the dominant structure is a cluster of m=10 particles with five-fold symmetry. At a particle level, we find three regimes for the crystallisation process: metastable fluid (dominated by m=10 clusters), crystal and a transition region of frequent hopping between crystal-like environments and other (m\neq10) structuresComment: 10 page