Third, we do not consider tilted ligand structures in our sandwich simulations. While it is well-known that alkanemonothiol ligands adapt a tilt angle (which we also find in our SAM simulations, see Section 3.1), it is not known from experiments how large the tilt angle of alkanedithiol ligands is, and whether ligands also tilt in GNP assemblies. Forming tilted sandwich structures turned out to be difficult in our simulations or resulted in poorly crosslinked interfaces (see Supporting Information, Section S2.3.1). Therefore, ligand molecules in our sandwich structures are non-tilted. Assuming that alkanedithiol ligands would also arrange in an ordered, tilted fashion, the surface-to-surface distance would be reduced. For example, a reduction of the surface-to-surface distance by ∼ 1.6 Å could be expected for a 30 °tilt angle compared to the surface-to-surface distance we obtain from our non-tilted sandwich structure, which would increase the deviation of our simulated surface-to-surface distance from our experimentally obtained interparticle distance of the larger particles, but at the same time reduce the deviation to the interparticle distance of the smaller particles (see Figure ). Furthermore, our MD simulations mainly result in lowest-energy structures with nontilted ligands in gauche conformations. In contrast, MD simulations of 3D networks of cross-linked GNPs by Yeh et al. 36,37 also included ligands in all-trans conformations at the equilibrium distance, especially at the edges of the facets (see Figure ). Based on their simulations, they suggested that these all-trans linkers were mainly responsible for the elasticity of the GNP films. While we have shown that the absence of facet edges and curvature does not result in interparticle distances that deviate significantly from experimental findings, future investigations of our model interfaces, especially in the presence of strain or analyte molecules, will be necessary to explore in more detail the limits of a "one-interface" approach to the properties of cross-linked GNP films.