Metal particles, surface plasmon effects

The excitation of the surface plasmon effect also induces strongly enhanced fluorescence properties of gold nanoparticles due to the enhanconent in the radiative rate of the inter-band electronic transitions relative to that in bulk metals. Metal nanoparticles, especially gold nanorods exhibit enhanced two-photon luminescence (TPL) and multi-photon luminescoice (MPL) [7, 8]. Strongly-enhanced TPL has been observed from individual particles [9, 10] and particle solutions [11] under femtosecond NIR laser excitation. This observation raises the possibility of nonlinear optical imaging in the NIR region, where water and biomolecules have... 

The presence of metallic surfaces or particles in the vicinity of a fluorophore can dramatically alter the fluorescence emission and absorption properties of the fluorophore. The effect, which is associated with the surface plasmon resonance of the metallic surface, depends on parameters such as metal type, particle size, fluorophore type and fluorophore-particle separation. 

A clear, commonly accepted terminology to describe few-atom subnanoscale metals exhibiting quantized energy levels is lacking. The lack of a coherent terminology leads to confusion and may hamper development. In this chapter, we restrict the term metal cluster to describe few-atom metals with discrete energy levels, and use metal nanoparticle, for particles that have surface plasmon resonance effects (approximate size range between 1 and 100 nm). 

For the same particles, the volume plasmon is located at very high energies (6-9 eV). The surface obviously plays a very important role for the observation of the surface plasmon resonance because it alters the boundary conditions for the polarizability of the metal and therefore shifts the resonance to optical frequencies. In this sense, the surface plasmon absorption is a small particle (or thin layer) effect but is definitely not a quantum size effect [14]. 

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. 

---