Spectrally Resolved Surface-Enhanced Raman Scattering Imaging Reveals Plasmon-Mediated Chemical Transformations

[Image: see text] Challenges investigating molecules on plasmonic nanostructures have limited understanding of these interactions. However, the chemically specific information in the surface-enhanced Raman scattering (SERS) spectrum can identify perturbations in the adsorbed molecules to provide insight relevant to applications in sensing, catalysis, and energy conversion. Here, we demonstrate spectrally resolved SERS imaging, to simultaneously image and collect the SERS spectra from molecules adsorbed on individual nanoparticles. We observe intensity and frequency fluctuations in the SERS signal on the time scale of tens of milliseconds from n-mercaptobenzoic acid (MBA) adsorbed to gold nanoparticles. The SERS signal fluctuations correlate with density functional theory calculations of radicals generated by the interaction between MBA and plasmon-generated hot electrons. Applying localization microscopy to the data provides a super-resolution spectrally resolved map that indicates the plasmonic-induced molecular charging occurs on the extremities of the nanoparticles, where the localized electromagnetic field is reported to be most intense.