FERROCYANIDE/FERRICYANIDE REDOX COUPLE
FREQUENCY GENERATION SPECTROSCOPY
OPTICALLY TRANSPARENT ELECTRODES
The partnering of electrochemical and spectroscopic methods into a single experiment can yield unprecedented insights into the behavior of redox active materials and into interfacial processes. The application of coupled electrochemical and spectroscopic techniques, collectively called spectroelectrochemistry, has grown dramatically over the past three decades to the point that almost every spectroscopic technique available has been applied under potential control. Spectroelectrochemistry has found application across diverse fields from materials science, corrosion, and electronics to biochemistry and its progress has tracked the advances in microscopy and other optical methods providing increasingly detailed insights into electrochemical processes in diverse environments. This chapter describes the experimental considerations and application of spectroelectrochemistry as applied specifically to optical spectroscopy. We describe the experimental demands of applying electrochemical control to spectroscopic experiments across the most common optical formats. We examine specific applications of absorbance, emission, and vibrational spectroscopies under electrochemical control across a range of of materials, including inorganic, supramolecular structures, and polymers. Application of both steady- state and timeresolved spectroscopies to spectroelectrochemistry are examined and finally we anticipate the growing application of spectroelectrochemistry to some of the most recent advances in optical methods, particularly super- resolution methods and single molecule methods.