SERS Detection of the Vibrational Stark Effect from Nitrile-Terminated SAMs to Probe Electric Fields in the Diffuse Double-Layer

Oklejas, Vanessa; Sjostrom, Chris; Harris, Joel M.

doi:10.1021/ja017656s

SERS Detection of the Vibrational Stark Effect from Nitrile-Terminated SAMs to Probe Electric Fields in the Diffuse Double-Layer

Journal Article · Wed Feb 20 23:00:00 EST 2002 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja017656s· OSTI ID:2480867

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

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

The vibrational Stark effect is observed in the surface-enhanced Raman scattering spectra of self-assembled monolayers functionalized with pendant nitrile groups. Stark tuning of the nitrile-stretching frequency serves as a localized probe of the electric field in the diffuse double layer of a SAM-modified electrochemical interface. Stark-tuning rates at low ionic strength correspond to reasonable values of the local electric (E) field in the double layer. The nitrile-stretching frequency converges on its isotropic value at applied potentials approaching the PZC, which indicates that Stark-tuning of the frequency is a direct probe of the E field at the interface. Loss of the local electric field at high ionic strengths shows that the probe responds to changes in the Debye length of the double layer. Furthermore, the results demonstrate the applicability of this electric-field probe for characterizing the diffuse double-layer region.

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:: 2480867

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 11 Vol. 124; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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