In the following, we will take a closer look at the ligands arrangement of 9DT cross-linked systems, as these ligands have been used previously for several interesting applications. The potential energy vs. surface-to-surface distance graph of a representative MD simulation of 9DT cross-linked surfaces is shown in During the simulations, some of the ligands partially dissociated from the surfaces. Overall, of 8 dithiol ligands in the simulation cell, an average of 7.15 ligands were bridging linkers, and 0.85 ligands were bound one-sided, while free linkers were not observed, resulting in a fraction of cross-linkers of 0.89. In contrast to Yeh et al. who observed a decrease of loop forming linkers and thereby an increase in cross-linkage with increasing chain length in their MD simulations of GNP assemblies of 4 nm sized GNPs using a united atom approach, a dependence of the cross-linkage on the alkane chain length was not observed in our simulations (see Supporting Information, Table ). Our fraction of bridging linkers for 9DT systems is also larger than in MD simulations by Yeh et al.. In that work, the authors found roughly the same fraction for bridging (0.56) and only one-side-bonded (0.43) 9DT ligands, with the remaining ligands being free ligands. The fraction of bridging linkers in our simulations was also much larger than in experimental studies on ∼ 3.2 nm large GNPs, cross-linked by alkanedithiols of different chain lengths. Schlicke et al. observed a ratio of GNP-bonded thiol groups to free thiol groups of 0.33. However, a rapid-layer-by-layer spin-coating method was used to prepare the films, which can cause trapping of dithiol cross-linkers, which are not bound with their thiol group to the GNPs, causing the low fraction of cross-linked ligands. In a similar study by Joseph et al. on alkanedithiol-cross-linked ∼ 4 nm large GNPs, produced with a layer-by-layer self-assembly method, a higher fraction of cross-linkers was observed. The authors obtained a fraction of ∼ 0.63 for double-side-bonded and ∼ 0.37 for single-side-bonded 9DT ligands, which is closer to our simulated results. Overall, a larger fraction of bridging ligands for our sandwich structures than in nanoparticle assemblies can be expected, since we are reducing the system to the interface between two particles (see Figure ), where most dithiol ligands are expected to interlink the surfaces, and we do not consider interstitial sites between the particles, where no second particle is nearby, and where naturally only one side of the dithiol ligand can be adsorbed. With increasing alkane chain length, an increase of the preferred surface-to-surface distance by 1.2 Å per carbon unit was found in our simulations (see Figure ). For comparison, small-angle X-ray scattering (SAXS) measurements reported by Schlicke et al. on thin films consisting of ∼ 3.2 nm large GNPs, cross-linked with alkanedithiols of different chain lengths, indicated an increase of ∼ 0.9 Å per carbon unit. Furthermore, the absolute values of our simulated surface-to-surface distances are in reasonable agreement with the experimental data. The calculated distance of 12.0 Å of the 9DT system, for example, is comparable to experimental distances of ∼ 3.2 nm large GNPs of 10.6 Å, keeping in mind that several approximations and uncertainties are involved.