Symmetry, equivalence, and molecular self-assembly

Molecular self-assembly at equilibrium is fundamental to the fields of biological self-organization, the development of novel environmentally responsive polymeric materials, and nanofabrication. Our approach to understanding the principles governing this process is inspired by existing models and measurements for the self-assembly of actin, tubulin, and the ubiquitous icosahedral shell structures of viral capsids. We introduce a family of simple potentials that give rise to the self-assembly of linear polymeric, random surface (membrane), tubular (nanotube), and hollow icosahedral structures that are similar in many respects to their biological counterparts. The potentials involve equivalent particles and an interplay between directional (dipolar, multipolar) and short-range (van der Waals) interactions. Specifically, we find that the dipolar potential, having a continuous rotational symmetry about the dipolar axis, gives rise to chain formation, while particles with multipolar potentials, having discrete rotational symmetries (square quadrupole or triangular ring of dipoles or hexapole), lead to the self-assembly of open sheet, nanotube, and hollow icosahedral geometries. These changes in the geometry of self-assembly are accompanied by significant changes in the kinetics of the organization.