Direct Determination of Plasmon Enhancement Factor and Penetration Depths in Surface Enhanced IR Absorption Spectroscopy.

Surface Enhanced Infrared Absorption Spectroscopy (SEIRAS) is a powerful tool for studying a wide range of surface and electrochemical phenomena. For most electrochemical experiments the evanescent field of an IR beam partially penetrates through a thin metal electrode deposited on top of an attenuated total reflection (ATR) crystal to interact with molecules of interest. Despite its success, a major problem that complicates quantitative interpretation of the spectra from this method is the ambiguity of the enhancement factor due to plasmon effects in metals. We developed a systematic method for measuring this, which relies upon independent determination of surface coverage by Coulometry of a surface-bound redox-active species. Following that, we measure the SEIRAS spectrum of the surface bound species, and from the knowledge of surface coverage, retrieve the effective molar absorptivity, ε. Comparing this to the independently determined bulk molar absorptivity leads us to the enhancement factor = ε/ε. We report enhancement factors in excess of 1000 for the C-H stretches of surface bound ferrocene molecules. We additionally developed a methodical approach to measure the penetration depth of the evanescent field from the metal electrode into a thin film. Such systematic measure of the enhancement factor and penetration depth will help SEIRAS advance from a qualitative to a more quantitative method.