Do multilayer crystals nucleate in suspensions of colloidal rods?
We study the isotropic-to-crystal transformation in a mixture of colloidal hard rods and nonabsorbing polymer using computer simulations. We determine the height of the nucleation barrier and find that the critical cluster consists of a single crystalline layer growing laterally for all polymer fugacities considered. At lower supersaturation, the free energy of a single hexagonally packed layer increases monotonically with size, while the nucleation barrier of a second crystalline layer is extremely high. Hence, the nucleation of multilayer crystals is never observed. Multilayer crystals form only in the spinodal decomposition regime, either where, in an intermediate stage, single crystalline membranes coalesce into multilayer clusters or where, at higher polymer fugacity, smaller clusters of rods stack on top of each other to form long filaments. Eventually, these transient structures evolve into a thermodynamically stable bulk crystal phase.
Patti
Alessandro
A
Debye Institute for NanoMaterials Science, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands.
Dijkstra
Marjolein
M