Molecular phosphorescence enhancement by the plasmon field of metal nanoparticles

A theoretical model is proposed that allows the estimation of the quantum yield of phosphorescence of dye molecules in the vicinity of plasmonic nanoparticles. For this purpose, the rate constants of the radiative and nonradiative intramolecular transitions for rhodamine 123 (Rh123) and brominated rhodamine (Rh123-2Br) dyes have been calculated. The plasmon effect of Ag nanoparticles on various types of luminescence processes has been studied both theoretically and experimentally. We show that in the presence of a plasmonic nanoparticle, the efficiency of the immediate and delayed fluorescence increases significantly. The phosphorescence rate of the rhodamine dyes also increases near plasmonic nanoparticles. The long-lived luminescence i.e., delayed fluorescence and phosphorescence is more enhanced for Rh123-2Br than for Rh123. The largest phosphorescence quantum yield is obtained when the dye molecule is at a distance of 4-6 nm from the nanoparticle surface. Our results can be used in the design of plasmon-enhancing nanostructures for light-emitting media, organic light-emitting diodes, photovoltaic devices, and catalysts for activation of molecular oxygen.