The excluded volume of hard sphero-zonotopes

Excluded volume effects can account for most ordering transitions in simple liquids and liquid crystals. Starting with the work of Onsager, this has been demonstrated in the case of liquid crystals for a number of simple convex bodies, e.g. sphero-cylinders, for which the orientation-dependent pair-excluded volume could be written down analytically. However, in recent years, experiments and simulations have been reported on ordering transitions in suspensions of more complex convex colloids. For these systems, theoretical understanding is hampered by the fact that no analytical expressions for the pair-excluded volume were available. Here we show that it is possible to obtain explicit expressions for the pair-excluded volume of a much larger class of convex bodies: the so-called sphero-zonotopes. These bodies are obtained by ‘padding’ a special class of convex polytopes with a blanket of uniform thickness. The resultant family of particles encompasses a wide range of shapes that have been considered as models for fluid and liquid crystalline behaviour e.g. spheres, cubes, sphero-cylinders, sphero-platelets. We discuss two explicit examples: sphero-cuboids, the 3D core generalization of the sphero-cylinder and the sphero-platelet, and hexagonal prisms that are models for the recently synthesized colloidal gibbsite platelets. Employing the fact that a cylinder is a zonoid, i.e. the limit of a sequence of right regular prisms, we are able to compute the excluded volume of the ‘true’ sphero-cylinder, a uniformly padded cylinder, of which the oblate-spherocylinder is a known example. Our approach en passant provides a relatively elementary rederivation of Onsager’s classical result on cylinders.