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This section highlights the use of iSEFMI for characterizing SAMs in which at least one of the adsorbates possesses a fluorescent moiety at their distal end (Fig. 11). This in situ spectroelectrochemical technique based on fluorescence takes advantage of the quenching of molecular fluorescence when near (in the nm range) a metallic surface (as discussed in Sect. 2) [59, 92]. Potential-induced changes in the separation of the fluorophore from the metal can be monitored by measuring fluorescence intensity.

Since the dimer fluorescence is observed through FRET from the monomer, it can also be inferred that the SAM is composed of a mixture of dimers and monomers in close proximity. , employing one set of filters per fluorophore studied) is that only one wavelength range can be measured at a given time. This renders any comparison sequential and relies on the similarity between the fabricated layers. An improvement to the setup could include the addition of a beamsplitter and the use of two cameras simultaneously.

The influence of the electrode potential on the interfacial properties of adsorbed molecules can be studied through the use of chemically specific analyses such as IR absorption which has enabled significant advances in understanding small molecule redox pathways [9]. , SEIRAS) [10, 11]. Other in situ FTIR approaches have used PMIRRAS to investigate the electrode surface, providing structural and orientation information as a function of potential [12–18]. Electrochemistry has been also coupled with methods sensitive to refractive index changes at the metal surface, such as ellipsometry and surface plasmon resonance [19–23].