Entropic effects in the self-assembly of open lattices from patchy particles

Open lattices are characterized by low-volume-fraction arrangements of building blocks, low coordination number, and open spaces between building blocks. The self-assembly of these lattices faces the challenge of mechanical instability due to their open structures. We theoretically investigate the stabilizing effects of entropy in the self-assembly of open lattices from patchy particles. A preliminary account of these findings and their comparison to experiment was presented recently [Mao, Chen, and Granick, Nat. Mater. 12, 217 (2013)]. We found that rotational entropy of patchy particles can provide mechanical stability to open lattices, whereas vibrational entropy of patchy particles can lower the free energy of open lattices and, thus, enables the selection of open lattices verses close-packed lattices which have the same potential energy. These effects open the door to significant simplifications of possible future designs of patchy particles for open-lattice self-assembly.