Several factors affect whether a single interface can be a good model for GNP assemblies (see Figure and the discussion in Section 3.2.1). Even though we cannot, therefore, exclude error cancellation, we find that a model focusing on a single, flat, interface can describe interparticle distances and charge transport in GNP assemblies with qualitative accuracy for monothiol capping, and even with quantitative accuracy for dithiol linkage. The focus on a single, flat, interface allows for a level of atomistic detail that would be hard or even impossible to achieve with larger models describing entire GNPs or their assemblies, which usually work with coarse-grained descriptions of the ligands. This focus allows for an in-depth exploration of the impacts of ligand arrangements, coverages, inter-linkage etc. on interparticle distance and conductance. Moreover, the scope of our studies can be broadened towards different ligands or ligand mixtures, including in combination with analyte molecules to assess their potential as sensors.