Real-space observation of far- and near-field-induced photolysis of molecular oxygen on an Ag(110) surface by visible light

Dissociation of molecular oxygen is an important elementary process in heterogeneous catalysis. Here, we report on a real-space observation of oxygen photolysis on the Ag(110) surface at 78 K by far- and near-field excitation in the ultraviolet-near-infrared range using a low-temperature scanning tunneling microscope (STM) combined with wavelength-tunable laser excitation. The photolysis of isolated oxygen molecules on the surface occurs even by visible light with the cross section of ∼10^-19 cm². Time-dependent density functional theory calculations reveal optical absorption of the hybridized O₂-Ag(110) complex in the visible and the near-infrared range which is associated with the oxygen photolysis. We suggest that the photolysis mechanism involves a direct charge transfer process. We also demonstrate that the photolysis can be largely enhanced in plasmonic STM junctions, and the cross section is estimated to be ∼10^-17 cm^-2 in the visible and the near-infrared range, which appears to be an interesting feature of plasmon-induced reactions from the perspective of photochemical conversion with the aid of solar energy.