Tip-Enhanced Multipolar Raman Scattering.

We record nanoscale chemical images of thiobenzonitrile (TBN)-functionalized plasmonic gold nanocubes via tip-enhanced Raman spectroscopy (TERS). The spatially averaged optical response is dominated by conventional (dipolar) TERS scattering from TBN but also contains weaker spectral signatures in the 1225-1500 cm-1 region. The weak optical signatures dominate several of the recorded single-pixel TERS spectra. We can uniquely assign these Raman-forbidden transitions to multipolar Raman scattering, which implicates spatially varying enhanced electric field gradients at plasmonic tip-sample nanojunctions. Specifically, we can assign observations of tip-enhanced electric dipole-magnetic dipole as well as electric dipole-electric quadrupole driven transitions. Multipolar Raman scattering and local optical field gradients both need to be understood and accounted for in the interpretation of TERS spectral images, particularly in ongoing quests aimed at chemical reaction mapping via TERS.