Potential-Dependent Surface-Enhanced Raman Scattering from Adsorbed Thiocyanate for Characterizing Silver Surfaces with Improved Reproducibility

Oklejas, Vanessa; Harris, Joel M.

doi:10.1366/0003702041655511

Potential-Dependent Surface-Enhanced Raman Scattering from Adsorbed Thiocyanate for Characterizing Silver Surfaces with Improved Reproducibility

Journal Article · Sun Aug 01 00:00:00 EDT 2004 · Applied Spectroscopy

DOI:https://doi.org/10.1366/0003702041655511· OSTI ID:2480868

Oklejas, Vanessa ^[1]; Harris, Joel M. ^[1]

University of Utah, Salt Lake City, UT (United States)

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. Furthermore, 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 SERS-active sites that exhibit strong charge-transfer interactions with the adsorbate and large chemical SERS enhancement.

View Accepted Manuscript (DOE)

Research Organization:: University of Utah, Salt Lake City, UT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG03-93ER14333

OSTI ID:: 2480868

Journal Information:: Applied Spectroscopy, Journal Name: Applied Spectroscopy Journal Issue: 8 Vol. 58; ISSN 0003-7028

Publisher:: Society for Applied SpectroscopyCopyright Statement

Country of Publication:: United States

Language:: English

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Potential-Dependent Surface-Enhanced Raman Scattering from Adsorbed Thiocyanate for Characterizing Silver Surfaces with Improved Reproducibility

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