Spatio-Spectral Characterization of Multipolar Plasmonic Modes of Au Nanorods via Tip-Enhanced Raman Scattering.

Tip-enhanced Raman (TER) spectral images of 4-thiobenzonitrile-coated Au nanorods map the spatial profiles and trace the resonances of dipolar and multipolar plasmonic modes that are characteristic of the imaged particles. For any particular rod, we observe sequential transitions between high-order modes at low frequency shifts and lower-order modes at higher frequencies. We also notice that higher-order modes (up to m = 4) are generally observed for long rods as compared to their shorter analogues, where longitudinal dipolar resonances (m = 1) are observable. In effect, this work adds a new dimension to local optical field mapping via TERS, which we have previously explored. Not only can the magnitudes, vector components, local/nonlocal characters of local optical fields be imaged through molecular TERS, but spatially varying local optical resonances are also direct observables.