MD simulations of flat gold surfaces with alkanemonothiolates and alkanedithiolates of different alkane chain lengths, ranging from 5 to 12 carbon units, were performed. Structures extracted from those simulations were then used for the charge transport calculations. Furthermore, to compare the simulated surface-to-surface distances with experimental data on larger particles than those documented in the literature, we prepared 9DT cross-linked films with 7.44 nm large GNPs and measured the interparticle distance using GISAXS (for details, see Supporting Information, Section S1.1).