Spectroelectrochemistry vibrational spectroscopy

Dederichs E, Eriedrich KA, Daum W. 2000. Sum-frequency vibrational spectroscopy of CO adsorption on Pt(lll) and Pt(llO) electrode surfaces in perchloric acid solution Effects of thin-layer electrol3des in spectroelectrochemistry. J Phys Chem B 104 6626-6632. 

The use of infrared spectroscopy, either through fingerprint characterisation or by functional group identification, is well established. IR vibrational spectroscopy has thus been applied in spectroelectrochemistry for quite some time. ° The possibility to establish the symmetry of a molecule has made IR-SEC a most valuable tool for mixed-valence chemistry, ° allowing intramolecular electron-transfer rates in the picosecond region to be assessed and electron-transfer isomers to be established. ... 

Vibrational spectroelectrochemistry has now almost superseded UV-vis spectroelectrochemistry as the most commonly reported method. Because vibrational spectroscopy can give structural information, it has found extensive application in the study of the double layer, redox products in solution, and surface adsorbed species. The two most prevalent vibrational spectroscopies applied to spectroelectrochemistry are Infrared and Raman. Though the underlying mechanism and theory of each technique is fundamentally different, both methods give detailed vibrational information which may be used in spectroelectrochemistry to determine and monitor structural changes accompanying electrochemical... 

C. Korzeniewski, Infrared spectroelectrochemistry, in Handbook of Vibrational Spectroscopy, J. C. Chalmers and P. R. Griffiths, Eds., Wiley, Chichester, West Sussex, England, 2002, Vol. 4, p. 2699. 

Spectroelectrochemistry encompasses a group of techniques that allow simultaneous acquisition of electrochemical and spectroscopic information in situ in an electrochemical cell. A wide range of spectroscopic techniques may be combined with electrochemistry, including electronic (UV-visible) absorption and reflectance spectroscopy, luminescence spectroscopy, infrared and Raman spectroscopies, electron spin resonance spectroscopy and ellipsometry. Molecular properties such as molar absorption coefficients, vibrational absorption frequencies and electronic or magnetic resonance frequencies, in addition to electrical parameters such as current, voltage or charge, are now being used routinely for the study of electron transfer reaction pathways and the fundamental molecular states at interfaces. In this article the principles and practice of electronic spectroelectrochemistry are introduced. 

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