ELECTROCHEMICAL ANALYSIS USING ANGULAR POLARIZATION MODULATED ATIR SPECTROMETRY AND FLUOROMETRY

The absence of suitable in situ methods for obtaining electrical (charge-potential) and chemical information at electrode/electrolyte interfaces has represented a serious experimental incapacity in a broad range of fundamental and applied areas. This paper addresses the use of attenuated total internal reflection spectrometry and total internal fluorometry in conjunction with system modulation, both electrical cell control and spatially selective optical polarization, to probe this experimentally difficult region. Although applications of these techniques to electrolyte/solid electrode interfaces under equilibrium conditions will be described, emphasis will be given to interfacial characteization under current densities that significantly depart from equilibrium. The experimental configurations and difficulties in such measurements will also be addressed.