The electrodynamic interactions which lead to surface-enhanced Raman scattering (SERS) also lead to dramatic changes in the intensities, spectra, and temporal behavior of the fluorescent emission of adsorbates on rough metal surfaces. Spectral shifts of the fluorescence of adsorbates on island films have been observed (a) by examining the emission from adsorbates on different substrates, (b) by a "photochemical holeburning" method, and (c) by measuring the temporal evolution of the fluorescent spectrum at very short times after laser excitation. The observed changes can be accounted for within the framework of the electromagnetic theory of SERS generalized to include the details of molecular resonances and relaxed emission processes.

The enhancement of Raman scattering (RS), resonance Raman scattering (RRS), and fluorescence from molecules adsorbed on silver-island films is reported. A heirarchy of enhancements is found: 105 for RS, 103 for RRS, and 0.1–10 for fluorescence, depending on the quantum yield of the free molecule. Using the framework of the electromagnetic theory of surface-enhanced Raman scattering, generalized to treat molecular resonance phenomena, we develop a unified picture of the role of the surface plasmon resonances, and the surface-induced damping, in the light scattering processes. The observed heirarchy of enhancements is shown to have important spectroscopic consequences.

The enhancements of normal Raman scattering, resonance Raman scattering, and fluorescence from molecules adsorbed on identical, well‐characterized, silver‐island films are reported. The enhancement arises from the electromagnetic interaction between the molecules and the electronic plasma resonance of the silver islands. A hierarchy of enhancement ratios is found, with typical values of 105 for RS, 103 for RRS and 10−1 to 10 for fluorescence, depending on the quantum yield of the molecular fluorescence. A model, developed on heuristic grounds and substantiated using the density matrix formalism, describes the light scattering processes and the effects of the plasma resonance. This model presents a unified picture of the surface‐induced enhancement effects and is consistent with the experimental values. The comparison of all the forms of optical scattering leads to a complete determination of the role of the plasma resonances in the various portions of the scattering process. The excitation of the electronic plasma resonance results in an increased local field at the molecules leading to an increased excitation or absorption rate. Similarly, the excitation of the plasma resonance by the molecular emission dipole results in an increase in the radiative decay rate. However, the electromagnetic coupling of the molecule to the plasma resonance also adds an additional damping channel which can result in a reduction of the absorption or excitation rate as well as the emission yield. The resultant balance of these processes leads to the hierarchy in the measured enhancements. The hierarchy of enhancements is also shown to have important spectroscopic consequences.