Raman line shifts of adsorbed molecules in surface Raman spectroscopy

Abstract

A general electromagnetic formulation for the calculation of the Raman line shifts in surface Raman scattering from adsorbed molecules is given. These shifts in our model arise from the electromagnetic interaction between the molecules and the metal. Assuming a Thomas-Fermi model for the metal, explicit results for shifts as a function of the distance of the molecules from the spherical metallic surface are presented. The deviations from the classical 1/d³ dependence are also discussed.