We recently found that crystallization of monodisperse hard spheres from the bulk fluid faces a much higher free energy barrier in four than in three dimensions at equivalent supersaturation, due to the increased geometrical frustration between the s
implex-based fluid order and the crystal [J.A. van Meel, D. Frenkel, and P. Charbonneau, Phys. Rev. E 79, 030201(R) (2009)]. Here, we analyze the microscopic contributions to the fluid-crystal interfacial free energy to understand how the barrier to crystallization changes with dimension. We find the barrier to grow with dimension and we identify the role of polydispersity in preventing crystal formation. The increased fluid stability allows us to study the jamming behavior in four, five, and six dimensions and compare our observations with two recent theories [C. Song, P. Wang, and H. A. Makse, Nature 453, 629 (2008); G. Parisi and F. Zamponi, Rev. Mod. Phys, in press (2009)].
The dynamical instability of rough hard-disk fluids in two dimensions is characterized through the Lyapunov spectrum and the Kolmogorov-Sinai entropy, $h_{KS}$, for a wide range of densities and moments of inertia $I$. For small $I$ the spectrum sepa
rates into translation-dominated and rotation-dominated parts. With increasing $I$ the rotation-dominated part is gradually filled in at the expense of translation, until such a separation becomes meaningless. At any density, the rate of phase-space mixing, given by $h_{KS}$, becomes less and less effective the more the rotation affects the dynamics. However, the degree of dynamical chaos, measured by the maximum Lyapunov exponent, is only enhanced by the rotational degrees of freedom for high-density gases, but is diminished for lower densities. Surprisingly, no traces of Lyapunov modes were found in the spectrum for larger moments of inertia. The spatial localization of the perturbation vector associated with the maximum exponent however persists for any $I$.
The smallest maximum kissing-number Voronoi polyhedron of 3d spheres is the icosahedron and the tetrahedron is the smallest volume that can show up in Delaunay tessalation. No periodic lattice is consistent with either and hence these dense packings
are geometrically frustrated. Because icosahedra can be assembled from almost perfect tetrahedra, the terms icosahedral and polytetrahedral packing are often used interchangeably, which leaves the true origin of geometric frustration unclear. Here we report a computational study of freezing of 4d hard spheres, where the densest Voronoi cluster is compatible with the symmetry of the densest crystal, while polytetrahedral order is not. We observe that, under otherwise comparable conditions, crystal nucleation in 4d is less facile than in 3d. This suggest that it is the geometrical frustration of polytetrahedral structures that inhibits crystallization.
