Surface-Enhanced Infrared Spectroscopy: The Origin of the Absorption Enhancement and Band Selection Rule in the Infrared Spectra of Molecules Adsorbed on Fine Metal Particles

Abstract

Infrared transmission spectra of molecules adsorbed on silver island films evaporated on CaF₂ have been investigated. The spectra are remarkably simple compared with those of the molecules in the solid state (KBr pellets). Only the vibrational modes which give dipole changes perpendicular to the metal surface are infrared active. In addition, their intensities are about 200 times larger than those of the free molecule. These results can be fully accounted for if the electric field which excites the surface molecule is perpendicular to the local surface of the metal islands and is stronger than the incident electric field. The origin of the absorption enhancement and the surface selection rule is discussed theoretically by using a classical electromagnetic model.