title: Symmetry considerations for the targeted assembly of entropically stabilized colloidal crystals via Voronoi particles.
abstract: The relationship between colloidal building blocks and their assemblies is an active field of research. As a strategy for targeting novel crystal structures, we examine the use of Voronoi particles, which are hard, space-filling particles in the shape of Voronoi cells of a target structure. Although Voronoi particles stabilize their target structure in the limit of high pressure by construction, the thermodynamic assembly of the same structure at moderate pressure, close to the onset of crystallization, is not guaranteed. Indeed, we find that a more symmetric crystal is often preferred due to additional entropic contributions arising from configurational or occupational degeneracy. We characterize the assembly behavior of the Voronoi particles in terms of the symmetries of the building blocks as well as the symmetries of crystal structures and demonstrate how controlling the degeneracies through a modification of particle shape and field-directed assembly can significantly improve the assembly propensity.
authors.affiliation: †Department of Physics ‡Applied Physics Program §Department of Chemical Engineering and ⊥Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States.
authors.forename: Benjamin A
authors.initials: BA
authors.lastname: Schultz
authors.affiliation: †Department of Physics ‡Applied Physics Program §Department of Chemical Engineering and ⊥Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States.
authors.forename: Pablo F
authors.initials: PF
authors.lastname: Damasceno
authors.affiliation: †Department of Physics ‡Applied Physics Program §Department of Chemical Engineering and ⊥Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States.
authors.forename: Michael
authors.initials: M
authors.lastname: Engel
authors.affiliation: †Department of Physics ‡Applied Physics Program §Department of Chemical Engineering and ⊥Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States.
authors.forename: Sharon C
authors.initials: SC
authors.lastname: Glotzer
keywords: Monte Carlo simulation; entropic forces; hard particles; particle design; self-assembly