Electroreflectance problems

As is widely known, bulk species which have chromophores that absorb in the UV-Vis can be analyzed quantitatively and qualitatively by this spectroscopy. The study of electrodes or species adsorbed as thin layers by UV-Vis is more difficult, due to sensitivity problems and the availability of the appropriate chromophores [50], Another use of this type of analysis is electroreflectance [51,52], Adsorption of species on reflective electrode surfaces changes their reflectivity. Thus, this method can indicate electroadsorption processes very sensitively, in situ, although it does not provide specific information on the structure and composition of surface layers. 

It is important to note in this context that electroreflectance measurements on silver electrodes (in the absence of pyridine) have found structures attributed to surface states, which were unusually and strongly dependent on the electric potential. Normally, we would expect the energies of species in the interface to change not more than the change in the electric potential. When these findings are further verified, they may turn out to be very important for understanding SERS and interface problems in general. 

Another important point of data analysis is to find a relation between the dielectric properties of the electrode-electrolyte interface and its microscopic characteristics. A rigorous treatment of this problem is rather complex and involves large-scale computer calculations. An alternative method is to use semi-phenomenological models which relate the behavior of the dielectric tensor components to different features of the electron spectrum of the system. The mechanisms responsible for modulated electroreflectance can be classified as those arising from the modulation of the electron density in the selvedge region of the electrode (plasma electroreflectance), and from those which are due to a modulation of both interband and intraband optical transi-... 

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