Ligand Interactions and Nanoparticle Shapes Guide the Pathways toward Interfacial Self-Assembly

Non-equilibrium molecular dynamics simulations are used to probe the driving forces behind the formation of highly ordered, epitaxially connected superlattices of polyhedral-shaped nanoparticles (NPs) at fluid-fluid interfaces. By explicitly modeling coarse-grained ligands that cap the NP surface, it is shown that differences in NP shapes and time-dependent facet-specific ligand densities give rise to drastically different transformation mechanisms. Our results indicate that the extent of screening of the inter-particle interactions by the surrounding solvation environment has a significant impact on reversibility and ultimately the coherence of the final two-dimensional superlattice obtained. For the particle shapes examined, a hexagonal pre-assembly and a square superlattice final assembly (upon preferential ligand desorption from {100} facets) were prevalent; however, cuboctahedral NPs formed intermediate epitaxially bonded branched clusters, which eventually grew and rearranged into a square lattice; in contrast, truncated octahedral NPs exhibited an abrupt rhombic-to-square transition driven by the clustering of their numerous {111}-ligands that favored the stacking of linear NP rods. To track the incipient order in the system, we also outline a set of novel order parameters that measure the local orientation alignment between nearest-neighbor pairs. The simulation protocols advanced in this work could pave the way forward for exploration of the vast phase space associated with the interfacial self-assembly of NPs.