Detection of short-lived electrogenerated species by Raman microspectrometry

Raman microprobe spectrometry has been applied to the characterization of unstable species generated electrochemically at a microelectrode (radius in the 10 microm range). The ability of the spectroelectrochemical method to detect short-lived intermediates is directly related to its capability to probe small volumes. Raman microprobe spectrometry is appropriate for electrochemical applications because it allows the analysis of approximately 1 microm3 of solution. In spectroelectrochemical experiments, such a volume corresponds to a reaction layer of 1 microm thickness. Potentially, this technique can allow the observation of species with lifetimes of the order of 1 ms. To enhance the capabilities of this spectroscopic technique, we utilized it in combination with steady-state voltammetry at a microelectrode, to increase the concentration of unstable intermediates near the electrode surface. To determine the detection limit of this combined technique, we varied the base concentration as a means for varying the lifetime the radical cation electrogenerated from 9,10-dichloroanthracene. Well-resolved resonance Raman spectra were obtained for this radical cation when the lifetime was > or = 0.1 ms. This short time resolution achieved with micro-Raman spectroelectrochemistry makes this technique a powerful tool for the characterization of short-lived intermediates that are generated electrochemically in solution.