Evolution of unoccupied resonance during the synthesis of a silver dimer on Ag(111)

Silver dimers were fabricated on Ag(111) by single-atom manipulation using the tip of a cryogenic scanning tunnelling microscope. An unoccupied electronic resonance was observed to shift toward the Fermi level with decreasing atom–atom distance as monitored by spatially resolved scanning tunnelling spectroscopy. Density functional calculations were used to analyse the experimental observations and revealed that the coupling between the adsorbed atoms is predominantly direct rather than indirect via the Ag(111) substrate. While the substrate influence is small owing to the surface-projected sp band gap, the direct interaction is most likely due to the large extension of the p wave functions at the adsorbate atoms contributing to the resonance.