Abstract
A detailed understanding of the interaction between molecules and plasmonic nanostructures is important for several exciting developments in (bio)molecular sensing and imaging, catalysis, as well as energy conversion. While much of the focus has been on the nanostructures that generate enhanced and nano-confined optical fields, we herein highlight recent work from our groups that uses the molecular response in surface and tip enhanced Raman scattering (SERS and TERS, respectively) to investigate different aspects of the local fields. TERS provides access to ultra-confined volumes, and as a result can further explore and explain ensemble-averaged SERS measurements. Exciting and distinct molecular behaviors are observed in the quantum limit of plasmons, including molecular charging, chemical conversion, and optical rectification. Evidence of multipolar Raman scattering from molecules additionally provides insights into the inhomogeneous electric fields that drive SERS and TERS and their spatial and temporal gradients. The time scales of these processes show evidence of cooperative nanoscale phenomena that altogether contribute to SERS and TERS.