Efficient Monte Carlo Simulation of Faceted Nanoparticles Using Analytical Interaction Potentials

Understanding how energetic interactions between faceted nanoparticles (NPs) drive their self-assembly into higher-order architectures is critical for controlling various properties of NP assemblies. Here, we integrate analytical potentials that capture orientation-dependent van der Waals interactions into a Monte Carlo simulation framework for fast and accurate modeling of NP self-assembly. By implementing virtual cluster moves in the framework, we overcome sampling limitations and account for size-dependent diffusion of clusters. Simulations using the analytical potentials are orders of magnitude faster than atomistic and coarse-grained models while producing correct assembly morphologies. Phase behavior calculations of faceted NPs with weak and strong interparticle attractions show that attraction enhances ordering and shifts isotropic-to-semiordered transitions to lower volume fractions, while semiordered-to-crystalline transitions remain largely entropy driven. Overall, this work highlights the importance of enthalpic interactions and the advantages of using analytical potentials for efficient simulations of faceted NPs.