Dynamics of Single-Molecule Dissociation by Selective Excitation of Molecular Phonons

Breaking bonds selectively in molecules is vital in many chemistry reactions and custom nanoscale device fabrications. The scanning tunneling microscope (STM) has proved to be an ideal tool to initiate and view bond-selective chemistry at the single-molecule level, offering opportunities for the further study of the dynamics in single molecules on metal surfaces. We demonstrate H─HS and H─S bond breaking on Au(111) induced by tunneling electrons using low-temperature STM. An experimental study combined with theoretical calculations shows that the dissociation pathway is facilitated by vibrational excitations. Furthermore, the dissociation probabilities of the two different dissociation processes are bias dependent due to different inelastic-tunneling probabilities, and they are also closely linked to the lifetime of inelastic-tunneling electrons. Combined with time-dependent ab initio nonadiabatic molecular dynamics simulations, the dynamics of the injected electron and the phonon-excitation-induced molecule dissociation can be understood at the atomic scale, demonstrating the potential application of STM for the investigation of excited-state dynamics of single molecules on surfaces.