Surface-Enhanced Raman Scattering Based Vibrational Stark Effect as a Spatial Probe of Interfacial Electric Fields in the Diffuse Double Layer

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

doi:10.1021/jp0344693

Surface-Enhanced Raman Scattering Based Vibrational Stark Effect as a Spatial Probe of Interfacial Electric Fields in the Diffuse Double Layer

Journal Article · Fri Jun 27 00:00:00 EDT 2003 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/jp0344693· OSTI ID:2480838

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

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

Potential-dependent surface-enhanced Raman scattering (SERS) spectra of the nitrile stretching mode were acquired from a series of monolayers composed of alkanethiols (HS(CH₂)_xCH₃, where 6 ≤ x ≤ 10) and mercaptododecanenitrile (HS(CH₂)₁₁CN). These spectra were used to investigate the diffuse double layer at a silver electrode interface modified with mixed self-assembled monolayers (SAMs). The alkanethiol species acts to dilute the nitrile-terminated thiol to isolate the nitrile reporter group within the diffuse double-layer region. Nitrile groups co-immobilized with shorter diluent alkanethiol chains are placed more deeply into the diffuse double layer (relative to the methyl terminus of the surrounding alkanethiol). Interfacial electric fields, measured using observed Stark tuning rates of the nitrile stretching frequency, were examined as a function of SAM composition to map the structure of the diffuse double-layer region versus distance from the SAM/solution interface. The trends in the experimental data are largely consistent with Gouy–Chapman theory, in which Stark tuning rates, and the interfacial electric fields from which they originate, depend on both distance of the probe from the electrode surface and the ionic strength of the aqueous phase. For measurements at the highest ionic strengths, the experimentally observed double layer appeared to extend further into solution than predicted by Guoy-Chapman theory, which is consistent with the finite size of hydrated ions and theoretical predictions of the effect of a hydrophobic interface on the structure of the adjacent water layer. Furthermore, the results demonstrate the ability of this spectroelectrochemical experiment to characterize diffuse double-layer structure at electrochemical interfaces on a subnanometer distance scale.

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:: 2480838

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 31 Vol. 107; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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