All MD simulations were carried out using the LAMMPS molecular dynamics simulator. Inspired by an approach for simulating molecular break-junction experiments with similar ligands, 48 a reactive force field was used in combination with parameters from Bae and Aikens, for systems consisting of Au, S, C, and H atoms, to model the interaction of the ligand molecules with each other and with the gold surface. By using a reactive force field, bond formation and bond breaking events and thereby ligand associations as well as dissociations could be simulated. Periodic boundary conditions were applied in x and y directions (along the gold surfaces) to prevent edge effects (e.g., ligands at the edge of the cell moving around the surface to its bottom side). Simulations were performed using a microcanonical (NVE) ensemble. MD simulations of SAMs were performed at 100 K, as dissociations of ligands or reactions of the free thiol groups in dithiol molecules (see Supporting Information, Section S2.4) occurred more frequently at higher temperatures.