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. These shifts are attributed to a vibrational Stark shift arising from rectification of the optical field, which gives rise to a DC potential on the surface. All three molecules showed CN Stark shifts on the plasmonic surfaces. P-mercaptobenzonitrile is observed to be a well-behaved probe of the electric field, providing a narrow spectral line, suggesting a more uniform orientation on the surface. The utility of p-mercaptobenzonitrile was demonstrated by successfully assessing the electric field between gold nanoparticles adsorbed to a monolayer of the nitrile on a flat gold surface. A model is presented where the Stark shift of the alkyl-nitrile probe can be correlated to optical field, providing an intensity independent measurement of the local electric field environment.

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. Our results indicate that molecules adsorbed to the nanostructures are selectively enhanced in the presence of competing molecules. This selective enhancement arises from controlled interactions between nanostructures, such as an isolated nanoparticle and a TERS tip. Complementary experiments suggest that shifts in the vibrational frequency of reporter molecules can be correlated to the electric field. Here we present a strategy that utilizes the controlled formation of coupled plasmonic structures to experimentally measure both the magnitude of the electric fields and the observed Raman scattering.