Plasmonic nanostructures dramatically alter the radiative and nonradiative properties of single molecules in their vicinity. This coupling-induced change in decay channels selectively enhances specific vibronic transitions, which can enable plasmonic control of molecular reactivity. Here, we report coupling-dependent spectral emission shaping of single Rhodamine 800 molecules in the vicinity of plasmonic gold nanorods. We show that the relative vibronic transition rates of the first two vibronic transitions of the spontaneous emission spectrum can be tuned in the weak coupling regime, by approximately 25-fold, on the single molecule level.
Keywords: Antenna Enhancement; Emission Spectroscopy; Local Density of States; Localization Microscopy; Nanoantenna; Plasmonics; Spectral Shaping; Superresolution; Vibronic Transition Rate.