Plasmon-Driven Chemistry in Ferri-/Ferrocyanide Gold Nanoparticle Oligomers: A SERS Study.

The plasmon-driven chemistry of ferri-/ferrocyanide ions inside surface-enhanced Raman spectroscopy (SERS) active hot spots associated with gold nanoparticle oligomers is studied with continuous wave (CW) pump-probe SERS. By comparing with solution-phase normal Raman spectra, the characteristic spectral variations observed upon 532 nm optical pumping can be attributed to an oxidation process that occurs on the surface species followed by desorption of the oxidized surface species from the gold nanoparticles. Interrogating the plasmon-driven processes over a wide range of temperatures reveals that neither process is purely driven by the thermal effects associated with the optical pumping, and the apparent activation energies of both steps are estimated based on semiquantitative SERS analysis. Our observation identifies a more detailed reaction pathway for this classic model system under considerably simplified reaction conditions, adding to the current mechanistic background for future plasmon-driven chemistry studies and applications.