A spherical model with directional interactions. I. Static properties

We introduce a simple spherical model whose structural properties are similar to the ones generated by models with directional interactions, by employing a binary mixture of large and small hard spheres, with a square-well attraction acting only between particles of different sizes. The small particles provide the bonds between the large ones. With a proper choice of the interaction parameters, as well as of the relative concentration of the two species, it is possible to control the effective valence. Here we focus on a specific choice of the parameters which favors tetrahedral ordering and study the equilibrium static properties of the system in a large window of densities and temperatures. Upon lowering the temperature we observe a progressive increase in local order, accompanied by the formation of a four-coordinated network of bonds. Three different density regions are observed: At low density the system phase separates into a gas and a liquid phase; at intermediate densities a network of fully bonded particles develops; at high densities-due to the competition between excluded volume and attractive interactions-the system forms a defective network. The very same behavior has been previously observed in numerical studies of nonspherical models for molecular liquids, such as water, and in models of patchy colloidal particles. Different from these models, theoretical treatments devised for spherical potentials, e.g., integral equations and ideal mode coupling theory for the glass transition, can be applied in the present case, opening the way for a deeper understanding of the thermodynamic and dynamic behavior of low valence molecules and particles. (c) 2007 American Institute of Physics.