Geometrical Frustration and Static Correlations in Hard-Sphere Glass Formers

We analytically and numerically characterize the structure of hard-sphere fluids in order to review various geometrical frustration scenarios of the glass transition. We find generalized polytetrahedral order to be correlated with increasing fluid packing fraction, but to become increasingly irrelevant with increasing dimension. We also find the growth in structural correlations to be modest in the dynamical regime accessible to computer simulations.Comment: 21 pages; part of the "Special Topic Issue on the Glass Transition

Decorrelation of the static and dynamic length scales in hard-sphere glass-formers

We show that in the equilibrium phase of glass-forming hard-sphere fluids in three dimensions, the static length scales tentatively associated with the dynamical slowdown and the dynamical length characterizing spatial heterogeneities in the dynamics unambiguously decorrelate. The former grow at a much slower rate than the latter when density increases. This observation is valid for the dynamical range that is accessible to computer simulations, which roughly corresponds to that of colloidal experiments. We also find that in this same range, no one-to-one correspondence between relaxation time and point-to-set correlation length exists. These results point to the coexistence of several relaxation mechanisms in the accessible dynamical regime of three-dimensional hard-sphere glass formers.Comment: 8 pages, 7 figure

Capillary Condensation and Interface Structure of a Model Colloid-Polymer Mixture in a Porous Medium

We consider the Asakura-Oosawa model of hard sphere colloids and ideal polymers in contact with a porous matrix modeled by immobilized configurations of hard spheres. For this ternary mixture a fundamental measure density functional theory is employed, where the matrix particles are quenched and the colloids and polymers are annealed, i.e. allowed to equilibrate. We study capillary condensation of the mixture in a tiny sample of matrix as well as demixing and the fluid-fluid interface inside a bulk matrix. Density profiles normal to the interface and surface tensions are calculated and compared to the case without matrix. Two kinds of matrices are considered: (i) colloid-sized matrix particles at low packing fractions and (ii) large matrix particles at high packing fractions. These two cases show fundamentally different behavior and should both be experimentally realizable. Furthermore, we argue that capillary condensation of a colloidal suspension could be experimentally accessible. We find that in case (ii), even at high packing fractions, the main effect of the matrix is to exclude volume and, to high accuracy, the results can be mapped onto those of the same system without matrix via a simple rescaling.Comment: 12 pages, 9 figures, submitted to PR

Single particle fluctuations and directional correlations in driven hard sphere glasses

Via event driven molecular dynamics simulations and experiments, we study the packing fraction and shear-rate dependence of single particle fluctuations and dynamic correlations in hard sphere glasses under shear. At packing fractions above the glass transition, correlations increase as shear rate decreases: the exponential tail in the distribution of single particle jumps broadens and dynamic four-point correlations increase. Interestingly, however, upon decreasing the packing fraction, a broadening of the exponential tail is also observed, while dynamic heterogeneity is shown to decrease. An explanation for this behavior is proposed in terms of a competition between shear and thermal fluctuations. Building upon our previous studies [Chikkadi et al, Europhys. Lett. (2012)], we further address the issue of anisotropy of the dynamic correlations.Comment: 8 pages, 10 figure

Digital predictions of complex cylinder packed columns

A digital computational approach has been developed to simulate realistic structures of packed beds. The underlying principle of the method is digitisation of the particles and packing space, enabling the generation of realistic structures. Previous publications [Caulkin, R., Fairweather, M., Jia, X., Gopinathan, N., & Williams, R.A. (2006). An investigation of packed columns using a digital packing algorithm. Computers & Chemical Engineering, 30, 1178–1188; Caulkin, R., Ahmad, A., Fairweather, M., Jia, X., & Williams, R. A. (2007). An investigation of sphere packed shell-side columns using a digital packing algorithm. Computers & Chemical Engineering, 31, 1715–1724] have demonstrated the ability of the code in predicting the packing of spheres. For cylindrical particles, however, the original, random walk-based code proved less effective at predicting bed structure. In response to this, the algorithm has been modified to make use of collisions to guide particle movement in a way which does not sacrifice the advantage of simulation speed. Results of both the original and modified code are presented, with bulk and local voidage values compared with data derived by experimental methods. The results demonstrate that collisions and their impact on packing structure cannot be disregarded if realistic packing structures are to be obtained