Inelastically tunneled electrons from the tip of a scanning tunneling microscope were used to induce S-S bond dissociation of a $({\mathrm{CH}}_3\mathrm{S}{)}_2$ and lateral hopping of a ${\mathrm{CH}}_3\mathrm{S}$ on Cu(111) at 4.7 K. Both experimental results and theoretical calculations confirm that the excitation mechanism of the vibrationally induced chemistry reflects the projected density of states of molecular orbitals that appear near the Fermi level as a result of the rehybridization of the orbitals between the adsorbed molecules and the substrate metal atoms.

• Received 1 February 2007

DOI:https://doi.org/10.1103/PhysRevLett.100.136104