Classical theory of light scattering by an adsorbed molecule. I. Theory

Abstract

We develop a classical theory for the intensity and the depolarization ratio of the light scattered (Raman or Rayleigh) by an absorbed molecule. It is assumed that the optical properties of the system can be described by the polarizability of the molecule and the dielectric constant of the two media. The presence of the surface modifies the field incident upon the molecule as well as the field emitted by the induced dipole. We compute these effects, exactly, by using a dyadic Green’s function method, and approximately, by using a perfect mirror model. The theory provides the angular distribution of the scattered radiation, and its polarization as a function of the polarization, the frequency and the direction of incidence of the incoming radiation, as well as of the dielectric properties of the metal and the position of the molecule with respect to the surface. We use these equations to analyze the possible sources for the experimentally observed enhancement of the scattering caused by the presence of the metallic surface.