This thesis is focused on the computational characterization of the atomic scale properties of supramolecular structures at surfaces by means of ab-initio density-functional theory (DFT) techniques, and proceed in parallel with the experimental activity of the Low Temperature Scanning Tunneling Microscopy (LT-STM) group at the IOM-CNR TASC Laboratory. In particular, the different roles played by native gold adatoms in the self-assembly of various molecular structures has been deeply analysed.
