The entropic bond in colloidal crystals.

A vast array of natural phenomena can be understood through the long-established schema of chemical bonding. Conventional chemical bonds arise through local gradients resulting from the rearrangement of electrons; however, it is possible that the hallmark features of chemical bonding could arise through local gradients resulting from nonelectronic forms of mediation. If other forms of mediation give rise to "bonds" that act like conventional ones, recognizing them as bonds could open new forms of supramolecular descriptions of phenomena at the nano- and microscales. Here, we show via a minimal model that crowded hard-particle systems governed solely by entropy exhibit the hallmark features of bonding despite the absence of chemical interactions. We quantitatively characterize these features and compare them to those exhibited by chemical bonds to argue for the existence of entropic bonds. As an example of the utility of the entropic bond classification, we demonstrate the nearly equivalent tradeoff between chemical bonds and entropic bonds in the colloidal crystallization of hard hexagonal nanoplates.