Multimodal coupling of optical transitions and plasmonic oscillations in rhodamine B modified gold nanoparticles.

The optical properties of a photoluminescent dye rhodamine B (RhB) interacting with gold nanoparticles (AuNP) have been investigated using plasmonic absorbance, fluorescence, and resonance elastic light scattering (RELS) spectroscopy. We have found that these interactions result in a multimodal coupling that influence optical transitions in RhB. In absorbance measurements, we have observed for the first time the coupling resulting in strong screening of RhB π-π* transitions, likely caused by a contact adsorption of RhB on a conductive surface of AuNP. The nanoparticles quench also very efficiently the RhB fluorescence. We have determined that the static quenching mechanism with a non-Förster fluorescence resonance energy transfer (FRET) from RhB molecules to AuNP is involved. The Stern-Volmer dependence F(0)/F = f(Q) shows an upward deviation from linearity, attributed to the ultra-high quenching efficiency of AuNP leading to the new extended Stern-Volmer model. A sharp RELS peak of RhB alone (λ(max) = 566 nm) has been observed for the first time and attributed to the resonance fluorescence and enhanced scattering. This peak is completely quenched in the presence of AuNP(22nm). Our quantum mechanical calculations confirm that the distance between AuNP surface and conjugated π-electron system in RhB is well within the range of plasmonic fields extending from AuNP. The optical transition coupling to plasmonic oscillations and the efficient energy transfer due to the interactions of fluorescent dyes with nanoparticles are important for biophysical studies of life processes and applications in nanomedicine.