Infrared absorption enhancement of monolayer species on thin evaporated Ag films by use of a Kretschmann configuration: Evidence for two types of enhanced surface electric fields

Abstract

Infrared absorption enhancement of m- and p-nitrobenzoic acid deposited on thin-evaporated silver films has been investigated using the Kretschmann's ATR coupling method. The absorption spectra provide direct evidence that enhancement is prominent only for vibrations of the first monolayer adsorbed on the Ag surface. It is shown that all of the vibrational modes observed obey the normal dipole selection rule. Moreover, it was found that there exist two types of absorption enhancement; the first is enhanced (∼300) by both p- and s-polarized radiation, and the second is enhanced (∼60) by p-polarized radiation alone. The Ag film thickness optimum is about 50 A in the former case and about 200 A in the latter. The enhancement insensitive to the polarization state of radiation can well be explained by the excitation of the transverse collective electron resonance of the Ag islands, whereas that obtained by p-polarized radiation may be due to the excitation of delocalized surface plasmons modified by surface roughness. The image-dipole effect may also be significant in the mechanisms.