Experimental correlation of electric fields and Raman signals in SERS and TERS.

Enhanced Raman scattering from plasmonic nanostructures associated with surface enhanced (SERS) and tip enhanced (TERS) is seeing a dramatic increase in applications from bioimaging to chemical catalysis. The importance of gap-modes for high sensitivity indicates plasmon coupling between nanostructures plays an important role. However, the observed Raman scattering can change with different geometric arrangements of nanoparticles, excitation wavelengths, and chemical environments; suggesting differences in the local electric field.

Alkyl-Nitrile Adlayers as Probes of Plasmonically Induced Electric Fields.

Vibrational Stark shifts observed from mercaptoalkyl monolayers on surface enhanced Raman (SERS) active materials are reported to provide a direct measurement of the local electric field around plasmonic nanostructures. Adlayers of CN, p-mercaptobenzonitrile, and n-mercaptobutylnitrile were adsorbed to a heterogeneous nanostructured Ag surface. The frequency of the CN moiety was observed to shift in a correlated fashion with the SERS intensity.