Plasmon-driven dimerization via S-S chemical bond in an aqueous environment

The surface-enhanced Raman scattering (SERS) spectra of thioanisole are experimentally investigated in an electrochemical environment in this study. Two Raman peaks, which depend strongly not only on electric potential but also on the local surface plasmon resonances (LSPR), have been observed. Theoretical calculations reveal that thioanisole is first dissociated from thiophenol via the S-CH3 bond; plasmons then drive the dimerisation of thiophenol via the S-S bond, which is strongly potential dependent. One Raman peak corresponds to the S-S vibrational mode of the thiophenol dimer, and the other corresponds to the asymmetric C-C stretching modes of the benzenyl of the thiophenol dimer. The potential-dependent two Raman modes is the potential-dependent dimerisation dynamics of thiophenol via the S-S bond. Our experimental findings provide insight into the structural elucidation of adsorbed molecules and molecular surface reaction dynamics.