Vibrational spectroscopy SERS

Carrasco Flores, E., M.M. Campos-VaUette, P. Leyton, G. Diaz Fleming, R.E. Clavijo, J.V. Garcia-Ramos, N. Inoslroza, C. Domingo, S. Sanchez-Cortes, and R. Koch (2003). Study of the interaction of pollutant nitro polycyclic aromatic hydrocarbons with different metallic surfaces by surface-enhanced vibrational spectroscopy (SERS and SEIR). / Phys. Chem. A. 107,9611. 

Some characteristics of, and comparisons between, surface-enhanced Raman spectroscopy (SERS) and infrared reflection-absorption spectroscopy (IRRAS) for examining reactive as well as stable electrochemical adsorbates are illustrated by means of selected recent results from our laboratory. The differences in vibrational selection rules for surface Raman and infrared spectroscopy are discussed for the case of azide adsorbed on silver, and used to distinguish between "flat" and "end-on" surface orientations. Vibrational band intensity-coverage relationships are briefly considered for some other systems that are unlikely to involve coverage-induced reorientation. 

The application of surface-enhanced Raman spectroscopy (SERS) for monitoring redox and other processes at metal-solution interfaces is illustrated by means of some recent results obtained in our laboratory. The detection of adsorbed species present at outer- as well as inner-sphere reaction sites is noted. The influence of surface interaction effects on the SER spectra of adsorbed redox couples is discussed with a view towards utilizing the frequency-potential dependence of oxidation-state sensitive vibrational modes as a criterion of reactant-surface electronic coupling effects. Illustrative data are presented for Ru(NH3)63+/2+ adsorbed electrostatically to chloride-coated silver, and Fe(CN)63 /" bound to gold electrodes the latter couple appears to be valence delocalized under some conditions. The use of coupled SERS-rotating disk voltammetry measurements to examine the kinetics and mechanisms of irreversible and multistep electrochemical reactions is also discussed. Examples given are the outer- and inner-sphere one-electron reductions of Co(III) and Cr(III) complexes at silver, and the oxidation of carbon monoxide and iodide at gold electrodes. 

R. A. Dluhy, S.M. Stephens, S. Widayatl and A.D. Williams, Vibrational Spectroscopy of Biophysical Monolayers. Applications of IR and Raman Spectroscopy to Biomembrane Model Systems at Interfaces, Spectrochim. Acta Part A51 (1995) 1413. (Review on biomembrane model systems studied by surface-sensitive vibrational spectroscopic methods. In particular the following methods are surveyed external reflectance IR spectroscopy, wave-guide Raman spectroscopy cmd SERS.)... 

Kudelski, A. (2008) In situ SERS smdies on the adsorption of tyrosinase on bare and alkanethiol-modified silver substrates. Vibrational Spectroscopy, 46, 34-38. 

The creation of backspillover oxidic oxygen upon positive current application has also been confirmed recently by means of in situ surface enhanced Raman spectroscopy (SERS) by Basini et al. They found that the Pt-backspillover oxygen bond has an unusually low vibrational frequency (150 to 200 cm ). ... 

---