Self-Assembly of Model Triblock Janus Colloidal Particles in Two Dimensions

J Chem Theory Comput. 2022 Mar 8;18(3):1870-1882. doi: 10.1021/acs.jctc.1c01116. Epub 2022 Feb 14.


A simplified two-dimensional effective-solvent model of triblock Janus particles, consisting of three interaction sites in a linear configuration, a core particle, and two particles modeling the attractive patches at the poles, is developed to study the mechanism of nucleation and self-assembly in triblock Janus particles. The potential energy parameters are tuned against phase transition temperatures and free energy barriers to the nucleation of crystalline phases, calculated from our previous detailed model of Janus particles. Vapor-liquid equilibria and critical temperatures are calculated by grand-canonical molecular dynamics simulations for particles of different patch widths. With metadynamics, phase equilibria, mechanism of nucleation, and free energy barriers to nucleation are investigated. The minimum free energy path to nucleation indicates two steps. The first step, with a higher free energy increase, consists of the densification of the fluid into a disordered cluster. In the second step, of a lower free energy barrier, the inner particles of the disordered cluster reorient to form a crystalline nucleus. This two-step mechanism of nucleation of a kagome lattice is in complete agreement with the experiment and with our previous simulations using a detailed model of Janus particles. Large systems at a slight supersaturation generate multiple crystalline domains, which are misaligned at the grain boundaries. In complete agreement with the experiment and with previous simulation results, we observe a two-step mechanism for crystal growth: melting of the smaller (less stable) crystallites to a fluid followed by recrystallization at the surface of neighboring bigger (more stable) crystallites. A comparison of the present softer modeling of a Janus particle with harder models in the literature for self-assembly of Janus particles indicates that softer potentials stabilize open lattices (e.g., kagome) more than dense lattices (e.g., hexagonal). Also, experimental locations of phase transition points and barrier heights to nucleation are better reproduced by the present model than by the existing simple models.