Interfacial structure of dimethylsulfoxide at Ag electrodes from surface enhanced Raman scattering and differential capacitance

Aijin Shen, Jeanne E Pemberton

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18 Citations (Scopus)

Abstract

Surface enhanced Raman scattering (SERS) and differential capacitance have been used to study interfacial structure in LiBr-containing dimethylsulfoxide (DMSO) at Ag electrodes. The potential-dependent orientation of this solvent is driven by interactions of the O atoms with the Ag surface at positive potentials and by interactions of the S atoms with the surface at negative potentials. Significant spectral changes are observed at potentials in the vicinity of the pzc indicating reorientation of interfacial solvent molecules. Evidence for unique potential-dependent interactions of Li+ and Br- with DMSO and trace amounts of H2O in the electrochemical interface have been uncovered on the basis of their spectral signatures. Potential-dependent molecular pictures of the interface in this system are proposed.

Original languageEnglish (US)
Pages (from-to)21-31
Number of pages11
JournalJournal of Electroanalytical Chemistry
Volume479
Issue number2
StatePublished - Dec 22 1999

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Dimethyl Sulfoxide
Raman scattering
Capacitance
Electrodes
Atoms
Molecules

Keywords

  • Electrochemical interface
  • Halide ion adsorption
  • Non-aqueous solutions
  • Surface enhanced raman scattering

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Analytical Chemistry
  • Electrochemistry

Cite this

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AU - Shen, Aijin

AU - Pemberton, Jeanne E

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N2 - Surface enhanced Raman scattering (SERS) and differential capacitance have been used to study interfacial structure in LiBr-containing dimethylsulfoxide (DMSO) at Ag electrodes. The potential-dependent orientation of this solvent is driven by interactions of the O atoms with the Ag surface at positive potentials and by interactions of the S atoms with the surface at negative potentials. Significant spectral changes are observed at potentials in the vicinity of the pzc indicating reorientation of interfacial solvent molecules. Evidence for unique potential-dependent interactions of Li+ and Br- with DMSO and trace amounts of H2O in the electrochemical interface have been uncovered on the basis of their spectral signatures. Potential-dependent molecular pictures of the interface in this system are proposed.

AB - Surface enhanced Raman scattering (SERS) and differential capacitance have been used to study interfacial structure in LiBr-containing dimethylsulfoxide (DMSO) at Ag electrodes. The potential-dependent orientation of this solvent is driven by interactions of the O atoms with the Ag surface at positive potentials and by interactions of the S atoms with the surface at negative potentials. Significant spectral changes are observed at potentials in the vicinity of the pzc indicating reorientation of interfacial solvent molecules. Evidence for unique potential-dependent interactions of Li+ and Br- with DMSO and trace amounts of H2O in the electrochemical interface have been uncovered on the basis of their spectral signatures. Potential-dependent molecular pictures of the interface in this system are proposed.

KW - Electrochemical interface

KW - Halide ion adsorption

KW - Non-aqueous solutions

KW - Surface enhanced raman scattering

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