Optical suppression of energy barriers in single molecule-metal binding.

Transient bonds between molecules and metal surfaces underpin catalysis, bio/molecular sensing, molecular electronics, and electrochemistry. Techniques aiming to characterize these bonds often yield conflicting conclusions, while single-molecule probes are scarce. A promising prospect confines light inside metal nanogaps to elicit in operando vibrational signatures through surface-enhanced Raman scattering. Here, we show through analysis of more than a million spectra that light irradiation of only a few microwatts on molecules at gold facets is sufficient to overcome the metallic bonds between individual gold atoms and pull them out to form coordination complexes. Depending on the molecule, these light-extracted adatoms persist for minutes under ambient conditions. Tracking their power-dependent formation and decay suggests that tightly trapped light transiently reduces energy barriers at the metal surface. This opens intriguing prospects for photocatalysis and controllable low-energy quantum devices such as single-atom optical switches.