This project is in the general field of analytical and surface chemistry and in the subfields of electrochemistry and spectroscopy. Two spectroscopic techniques will be employed to probe electrode surfaces and nearby solutions. Spatially resolved absorption spectroscopy will be employed to examine reactions of electrochemically generated species, particularly those undergoing catalytic oxidation-reduction reactions. In addition, this technique will be employed to study diffusion to cylindrical microelectrodes and to electrodes of unusual geometry. Generation of optical gain in electro- chemiluminescent systems will be attempted. Raman spectroscopy will be employed to obtain structural information about electrogenerated species and to probe the surface of carbon electrodes. The carbon surface spectrum will be correlated with the electrochemical behavior of the material. The structure of surface oxides on modified carbon electrodes also will be examined. Spectroelectrochemical investigations of the electrode-solution interface will enable correlation of the molecular surface states of electrodes with their electron transfer characteristics and thereby lead to a better understanding of heterogeneous electron transfer reactions at the molecular level. Spatially resolved spectroelectrochemical studies will provide an experimental test of computer simulations of complex electrochemical reaction mechanisms and of diffusion at electrodes with unusual geometries.
