Investigations of the optical properties of thin, highly absorbing films under attenuated total reflection conditions: Leaky waveguide mode distortions.

Spectra of thin highly absorbing Nafion films doped with Ru(bpy)(3)(2+) on SF11 glass substrates were studied by internal reflection spectroscopy using a single reflection configuration. For the system under study, two modes of light interaction with the film are available: attenuation due to evanescent wave penetration and light propagation within the absorbing film. Unlike evanescent wave spectroscopy, light propagation within the film causes distortions in the measured spectra due to leaky waveguide propagation modes. Upon light propagation in a film doped with Ru(bpy)(3)(2+) spectral shifts up to 50nm to longer wavelengths can occur and additional absorbance peaks can appear in the spectra. These film-based distortions depend on the complex refractive index, the thickness of the film and the angle of incidence. These effects become significant for an extinction coefficient above 0.01 and a film thickness above 200nm. It is shown that spectral distortions can lead to quite complex dynamics in the internal reflection spectra upon analyte preconcentration in the film. Ru(bpy)(3)(2+) partitioning into the Nafion film causes significant refractive index changes that in turn alter leaky waveguide mode conditions in the film and, can even lead to a reduction of measured absorbance despite the increase in the extinction coefficient of the film.