Adsorbate motions induced by inelastic-tunneling current: theoretical scenarios of two-electron processes

We discuss how the excitation of high-frequency modes in adsorbed molecules may result in motion (e.g., rotation, translation, or dissociation) of the molecules. Our study is based on rate equations and considers one- and two-vibrational excitation processes, corresponding to linear and quadratic dependences of the reaction rate on the tunneling current in the case the scanning tunneling microscopy is used to excite the vibrations (inelastic tunneling). From the results reported in this paper it should be possible to obtain intramolecular transition rates directly from the experimental data, and gain some understanding on how these important quantities depend on the modes involved and on the substrate.