On the Nature of the Entropic Bond
Entropy is typically associated with disorder; yet, the counterintuitive notion that particles with no interactions other than excluded volume might self-assemble from a fluid phase into an ordered crystal has been known since the mid-20th century. First predicted for rods, and then spheres, the thermodynamic ordering of hard shapes by nothing more than crowding is now well established. In recent years, surprising discoveries of entropically ordered colloidal crystals of extraordinary structural complexity have been predicted by computer simulation and observed in the laboratory. Colloidal quasicrystals, clathrate structures, and structures with large and complex unit cells typically associated with metal alloys, or obtained in systems of interacting nanoparticles, can all self-assemble from disordered phases of identical particles due solely to entropy maximization. In this talk, we show how entropy alone can produce order and complexity beyond that previously imagined, both in colloidal crystal structure as well as in the kinetic pathways connecting fluid and crystal phases. We show how entropic forces can be directional and introduce the concept of the entropic bond. We introduce a new theory of entropic bonding and show how methods used by the quantum community to predict atomic crystal structures can be used to predict entropic colloidal crystals.