With increasing coverage of alkanemonothiolate ligands, going from single ligand per unit cell to a fully covered monolayer structure, a conversion of ligands from a "laying-down" to a "standing-up" phase has been observed in experiments. was not found at any coverage in our simulations. The upright-standing structure is similar to the commonly reported ( √ 3 × √ 3) R30°structure of alkanemonothiols on Au(111). Our fully covered unit cell consists of 8 ligands with a S-S spacing between adjacent ligands of 4.9 Å, which is consistent with a spacing of ∼ 5 Å as reported for experimental data in the literature. We found an average S-Au bond distance of 2.73 ± 0.02 Å, which is in agreement with DFT calculations and MD simulations 36,46 using a united-atom approach in combination with Lennard-Jones interaction potentials.