Keep Your Hair On—The Role of Dynamic Ligand Coverage in Nanoparticle Self-Assembly

The self-assembly of nanoparticles into ordered structures offers a powerful approach to creating materials with customizable properties. Central to these processes are organic ligands that coat nanoparticle surfaces, preventing uncontrolled aggregation and guiding the formation of superstructures with different types of translational and rotational order. However, the impact of ligand surface coverage on self-assembly, along with the dynamic adsorption and desorption processes that maintain ligand equilibrium between the nanoparticle surface and surrounding solution, is less well understood. In this study, we employ coarse-grained modeling and computer simulations to uncover the interplay of entropic and energetic forces driving ligand attachment. Our findings demonstrate that dynamic ligand coverage and desorbed ligands can play a pivotal role in dictating the thermodynamic stability of both common and more exotic nanoparticle superlattices.