Transport calculations were performed using self-consistent DFTB electronic structure calculations combined with a Landauer coherent tunneling approach using Green's functions, as implemented in DFTB+. Six additional layers of gold were added to each 3-layered gold surface to form the contact region. In structures where ligands dissociated from the surface during the MD simulation, hydrogen atoms were added to the free thiolate groups for the transport calculations. This was done as free thiolate groups caused artefacts in some charge transport calculations. In those calculations, the transmissions deviated from the structures without free thiolate groups by several orders of magnitudes (see Supporting Information, Table ). The threshold for counting ligands as dissociated was set to a S-Au distance larger than 3 Å, which is slightly more than the sum of their atomic radii.