Quantum yields nanoparticles, fluorescent quenching

Understanding the field enhancement of radiative rates is insufficient to predict how molecular photophysical properties such as enhancement of fluorescence quantum yield will be affected by interactions of the molecule with plasmons. A more detailed model of the photophysics that accounts for non-radiative rates is necessary to deduce effects on photoluminescence (PL) yields. Such a model must include decay pathways present in the absence of metal nanoparticles as well as additional pathtvays such as charge transfer quenching that are associated with the introduction of the metal particles. Schematically, we depict the simplest conceivable model in Figure 19. IB. Note that both the contributions of radiative rate enhancement and the excited state quenching by proximity to the metal surface will depend on distance of the chromophore from the metal assembly. In most circumstances, one expects the optimal distance of the chromophores from the surface to be dictated by the competition between quenching when it is too close and reduction of enhancement when it is too far. The amount of PL will be increased both due to absorption enhancement and emissive rate enhancement. Hence, it is possible to increase PL substantially even for molecules with 100 % fluorescence yield in the absence of metal nanoparticles. 

The quenched quantum yield and shortened lifetime of the dyes strongly indicated a direct bonding between the functional group of the nanoparticles and the fluorescent molecules... 

In two more recent papers on single molecule fluorescence near thin metallic layers, Enderlein reminds us that the quenching by metal nanoparticles shortens the lifetime of the excited state and by doing this, increases the number of excitation cycles that the molecule can survive before it is photobleached. This is an extremely important point, especially when dealing with single molecules, as fluorescence quantum yields are not nearly as important as the number of photons that are emitted before photobleaching occurs. 

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