The correlation between film thickness and adsorbate line shape in surface enhanced infrared absorption

Various experimental results on surface enhanced infrared absorption reveal asymmetric line shapes. Whereas the order of magnitude of the enhancement can be understood from electromagnetic field enhancement the unusual line shape remains without satisfactory explanation. An interaction with electron-hole pairs would lead to an asymmetric line but this should be restricted to the first monolayer. However, asymmetry is also observed for vibrations at larger distances from the metal-film surface. Here we show strongly asymmetric lines and their enhancement as a consequence of the interaction of adsorbate vibrations with surface plasmons of metal islands. Both the effects and also the baseline change can be estimated by a proper application of well established effective-media models. (C) 2003 American Institute of Physics.