Theory and simulation of ligand functionalized nanoparticles - a pedagogical overview

Synthesizing reconfigurable nanoscale synthons with predictive control over shape, size, and interparticle interactions is a holy grail of bottom-up self-assembly. Grand challenges in their rational design, however, lie in both the large space of experimental synthetic parameters and proper understanding of the molecular mechanisms governing their formation. As such, computational and theoretical tools for predicting and modeling building block interactions have grown to become integral in modern day self-assembly research. In this review, we provide an in-depth discussion of the current state-of-the-art strategies available for modeling ligand functionalized nanoparticles. We focus on the critical role of how ligand interactions and surface distributions impact the emergent, pre-programmed behaviors between neighboring particles. To help build insights into the underlying physics, we first define an "ideal" limit - the short ligand, "hard" sphere approximation - and discuss all experimental handles through the lens of perturbations about this reference point. Finally, we identify theories that are capable of bridging interparticle interactions to nanoscale self-assembly and conclude by discussing exciting new directions for this field.