Surface enhanced Raman spectroscopy of the silver/KCl, triethylenediamine (DABCO), water system

Abstract

1,4-Diazabicyclo[2.2.2]octane, (N(CH 2CH 2) 3N), usually abbreviated DABCO or DBO, is a symmetric top molecule of point group D 3h. SERS experiments have been carried out in an optical electrochemical cell using a silver electrode roughened by a single oxidation-reduction cycle (ORC). The observed SERS spectra contained four strong bands at 624, 798, 990 and 1351 cm −1, all A' 1 totally symmetric modes. The same bands were also observed in SERS spectra of DABCO adsorbed on colloidal gold. In the electrochemical experiments, the maximum of SERS-intensity versus electrode potential plots was observed to shift to less negative potentials as the wavelength of the exciting line was shifted to the red. The radically-altered, relative intensities of the observed bands, as well as observed changes in relative intensity as a function of electrode potential, have been interpreted as a selective enhancement of those normal modes which have as a major component of vibrational motion the C-C stretch. These observations are correlated with current theories concerning the SERS mechanism, especially those involving charge transfer (CT).