Mechanisms enhanced Raman

Recent developments in the mechanisms of corrosion inhibition have been discussed in reviews dealing with acid solutions " and neutral solu-tions - . Novel and improved experimental techniques, e.g. surface enhanced Raman spectroscopy , infrared spectroscopy. Auger electron spectroscopyX-ray photoelectron spectroscopyand a.c. impedance analysis have been used to study the adsorption, interaction and reaction of inhibitors at metal surfaces. 

In most work on electrochemical systems, use is made of two effects that greatly enhance the Raman signals. One is resonance Raman spectroscopy (RRS), wherein the excitation wavelength corresponds to an electronic transition in an adsorbed molecule on an electrode surface. The other effect is surface-enhanced Raman spectroscopy (SERS), which occurs on certain surfaces, such as electrochemically roughened silver and gold. This effect, discovered by Fleischmann et al. (1974), yields enhancements of 10 to 10 . The vast majority of publications on Raman studies of electrochemical systems use SERS. The limitations of SERS are that it occurs on only a few metals and the mechanism of the enhancement is not understood. There is speculation that only a small part of the surface is involved in the effect. There is a very good review of SERS (Pemberton, 1991). 

Tolia, A. A., Williams, C. T., Weaver, M. J. et al. (1995) Surface-enhanced Raman spectroscopy as an in situ real-time probe of catalytic mechanisms at high gas pressures. The NO-H2 reaction on rhodium , Langmuir, 11, 3438. 

The relative importance of the two mechanisms - the non-local electromagnetic (EM) theory and the local charge transfer (CT) theory - remains a source of considerable discussion. It is generally considered that large-scale rough surfaces, e.g. gratings, islands, metallic spheres etc., favour the EM theory. In contrast, the CT mechanism requires chemisorption of the adsorbate at special atomic scale (e.g. adatom) sites on the metal surface, resulting in a metal/adsorbate CT complex. In addition, considerably enhanced Raman spectra have been obtained from surfaces prepared in such a way as to deliberately exclude one or the other mechanism. 

Fortunately, in favorable cases enhancement mechanisms operate which increase the signal from the interface by a factor of 105 — 106, so that spectra of good quality can be observed - hence the name surface-enhanced Raman spectroscopy (SERS). However, these mechanisms seem to operate only on metals with broad free-electron-like bands, in particular on the sp metals copper, silver and gold. Furthermore, the electrodes must be roughened on a microscopic scale. These conditions severely limit the applicability of Raman spectroscopy to electrochemical interfaces. Nevertheless, SERS is a fascinating phenomenon, and though not universally applicable, it can yield valuable information on many interesting systems, and its usefulness is expected to increase as instrumentation and preparation techniques improve. 

Kambhampati, R, Child, C. M., Foster, M. C., and Campion, A. 1998. On the chemical mechanism of surface enhanced Raman scattering Experiment and theory. J. Chem. Phys. 108 5013-26. 

The mechanism of C02 reduction to methane at Cu electrodes has been proposed by various groups [72-74], most of which involved the splitting of adsorbed CO followed by the hydrogenation of surface C atoms. When DeWulf et al. used X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy to study the reaction [72], they observed surface-bound carbenes (Cu CH2) as an intermediate in the system. Likewise, others used both in situ infrared (IR) reflection absorption spectroscopy and surface-enhanced Raman spectroscopy to observe the initial product of C02 reduction on Cu [74]. Typically, two different linearly bound CO species were identified and attributed to adsorption on either surface defect sites or terraces. 

Intracellular surface-enhanced Raman imaging has been reviewed by Chourpa and colleagues [23]. For intracellular measurements SERS provides a mechanism for enhancement of the signals from very small amounts of cell constituents, such as DNA, or pharmaceuticals. Typically colloidal silver or... 

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. 

Results will be split into various sections the first of which will be fundamentals of hot spots. This will include a summary of the most important developments in the theory of SERS hot spots for both the EM and CT enhancement mechanisms. The second section will cover developments in tip-enhanced Raman spectroscopy (TERS) which represents the idealized hot spot. Then some issues regarding hot spots and the single molecule will be tackled such as the magnitude of enhancement required for single-molecule detection, the effects of molecular orientation with respect to the hot spot as well as the possible influence of optical forces. Sections 4.4 and 4.5 will cover developments in the imaging and fabrication of SERS hot spots, respectively, which have important implications for theoretical modeling as well control of SERS hot spots. The chapter will conclude by summarizing some of the applications of SERS hot spots that have been recently reported. 

Kozich V, Wemcke W (2010) The vibrational pumping mechanism in surface-enhanced Raman scattering a subpicosecond time-resolved study. J Phys Chem C 114(23) 10484-10488... 

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