We provide the theoretical framework to understand the phenomenology and statistics of single-molecule (SM) signals arising in Surface-Enhanced Raman Scattering (SERS) under the presence of so-called electromagnetic hot-spots (HS's). We show that most characteristics of the SM-SERS phenomenon can be tracked down to the presence of tail-like (power law) distribution of enhancements and we propose a specific model for it. We analyze, in the light of this, the phenomenology of SM-SERS and show how the different experimental manifestations of the effect reported in the literature can be analyzed and understood under a unified ``universal'' framework with a minimum set of parameters.
Categories: physics.chem-ph physics.optics