Resonance Raman spectroelectrochemistry (RRSE) is applied for the first time to the study of a laser-driven photoelectrochemical process at a III-V semiconductor in nonaqueous solution. The specific system investigated is the one-electron photooxidation of tetrathiafulvalene (TTF) to form the corresponding cation radical (TTF+·) at n-type GaAs(100) in acetonitrile solution. Resonance Raman spectra (RRS) of TTF+· excited into both electronic excited states accessible to visible lasers as well as millisecond time scale resonance Raman intensity (RRI) vs. time transients are reported. Both the spectra and transients represent the detection of TTF+· in the diffusion layer adjacent to the electrode surface rather than in the bulk of solution.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry