Turning our attention to SAM sandwich structures, we investigated the change of the interparticle distance with increasing chain length of the ligands. We found an increase of 1.2 Å and 1.1 Å per carbon unit for alkanedithiolates and alkanemonothiolates, respectively, closely mirroring experimental findings. The simulated interparticle distance of a nonanedithiolate interface aligned well with the distance we measured for assemblies involving larger particles (approximately 7.4 nm) using GISAXS. By contrast, the experimental distance of smaller dithiol-linked particles (approximately 3.2 nm) was by about 1.5 to 2 Å lower. The calculated surface-to-surface distances of monothiolate sandwich structures deviated more significantly from experimental distances from the literature (underestimating it by about 5 Å). This deviation may be related to the difficulty of estimating proper surface coverage in the monothiolate layers on the two opposing gold surfaces and the resulting degree of interlacing.