Authors: Oklejas, Vanessa; Harris, Joel M.

Source: Applied Spectroscopy, Volume 58, Issue 8, Pages 220A-244A and 887-1022 (August 2004) , pp. 945-951(7)

Publisher: Society for Applied Spectroscopy

Abstract:

Surface-enhanced Raman scattering (SERS) spectroelectrochemistry is used to characterize electrochemically roughened and highly polished polycrystalline silver SERS-active substrates. Changes in the nitrile stretching vibrational mode of adsorbed thiocyanate are used as an in situ spectroscopic probe: the potential dependence of band position (Stark tuning), shape, and scattering intensity of this mode are measured in order to investigate differences between SERS-active sites found on smooth and roughened electrode surfaces. Results obtained from thiocyanate adsorbed onto two different types of highly polished Ag surfaces (alumina and diamond polishing) show discrete populations of SERS-active adsorption sites that remain stable over a wide potential range. This behavior stands in contrast to that observed on electrochemically roughened surfaces, where very strong Stark tuning, large vibrational bandwidths, and irreversible loss of SERS enhancement upon negative potential excursions can be attributed to a diverse population of labile SERSactive sites that exhibit strong charge-transfer interactions with the adsorbate and large chemical SERS enhancement.

Keywords: SURFACE-ENHANCED RAMAN SCATTERING; SERS; SPECTROELECTROCHEMISTRY; VIBRATIONAL STARK EFFECT

Document Type: Research article

DOI: http://dx.doi.org/10.1366/0003702041655511

Affiliations: 1: Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112-0850

Publication date: 2004-08-01

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