However, GNP assemblies, as studied by Yeh et al., 36 consist of up to 150000 atoms. Hence, methods like density functional tight binding (DFTB) can not be applied to study the charge transport features of the films, as computational times would be beyond feasible. To reduce the system size, and thereby the computational costs, we investigate whether the properties of GNP assemblies can be studied by considering just one cross-linked interface between flat gold surfaces, since such interfaces dominate the charge transport in the films. Jiménez et al. or Djebaili et al., who compared the surface coverages of single gold nanocrystals and flat Au(111) surfaces using atomistic MD simulations, already showed that the surface coverage of nanocrystals approaches that of flat surfaces with increasing particle size (see Supporting Information, Section S1.4 for further background), indicating that our approximation of the interfaces of GNP assemblies as interlinked Au(111) surfaces is reasonable especially for larger GNPs. We investigate structural properties, such as the interparticle distance of interfaces of alkanemonothiolate or alkanedithiolate ligands with different chain lengths with MD simulations and a reactive force field on an atomistic level and show that good (and, for dithiols, even quantitative) agreement with experimental observations can be achieved.