A theory of entropic bonding

Entropy alone can self-assemble hard nanoparticles into colloidal crystals of remarkable complexity whose structures are the same as atomic and molecular crystals, but with larger lattice spacings. Molecular simulation is a powerful tool used extensively to study the self-assembly of ordered phases from disordered fluid phases of atoms, molecules, or nanoparticles. However, it is not yet possible to predict colloidal crystal structures a priori from particle shape as we can for atomic crystals from electronic valency. Here, we present such a first-principles theory. By calculating and minimizing excluded volume within the framework of statistical mechanics, we describe the directional entropic forces that collectively emerge between hard shapes, in familiar terms used to describe chemical bonds. We validate our theory by demonstrating that it predicts thermodynamically preferred structures for four families of hard polyhedra that match, in every instance, previous simulation results. The success of this first-principles approach to entropic colloidal crystal structure prediction furthers fundamental understanding of both entropically driven crystallization and conceptual pictures of bonding in matter.