We examine the classical energy-balance equation for a fluorescing system consisting of a molecule near a small, spherical metal particle capable of sustaining electromagnetic resonances and irradiated with laser light. From the energy-flow distribution in the entire system, we obtain the enhancement factor for the fluorescence emission of the adsorbed molecule. Numerical results demonstrate that the electromagnetic interactions of the molecule and the surface can be understood in terms of energy flow through the entire system and applied to investigate spectroscopic properties of adsorbates in similar systems. Absorption and emission rates of the adsorbed molecule are determined considering the energy-flow distribution and its dependence on the substrate as well as molecular parameters. Such understanding is useful in predicting spectroscopic responses of adsorbates.
Physical Review B
Phys. Rev. B 65 155416 (2002)