TY - JOUR
T1 - Surface Raman scattering of interfaces at Ag electrodes emersed from dimethylsulfoxide
T2 - Spectroscopic evidence for an emersion-induced potential shift
AU - Shen, Aijin
AU - Pemberton, Jeanne E.
N1 - Funding Information:
The authors gratefully acknowledge support of this work by the National Science Foundation (CHE-9504345.) The authors also express their sincerest gratitude to Dr Derek E. Gragson and Dr Geraldine L. Richmond of the University of Oregon for their sum-frequency generation measurements on DMSO.
Copyright:
Copyright 2020 Elsevier B.V., All rights reserved.
PY - 1999/12/22
Y1 - 1999/12/22
N2 - Surface Raman scattering has been used to study Ag electrodes emersed from LiBr solutions of dimethylsulfoxide (DMSO). Interfacial DMSO structure is generally similar to that in-situ, although spectral evidence for an emersion-induced potential shift is observed. The DMSO orientation at Ag electrodes is driven by interaction of the oxygen atom at potentials positive of the potential of zero charge (pzc) and the sulfur atom at potentials negative of the pzc. Pronounced restructuring of DMSO occurs in the vicinity of the pzc. Specific interactions between DMSO and electrolyte ions are clearly detected in the emersed interface. The observed potential shift is attributed to reorientation of the DMSO solvent dipoles at the emersed layer | gas interface. These results represent the first spectroscopic evidence for the existence of an emersion-induced potential shift.
AB - Surface Raman scattering has been used to study Ag electrodes emersed from LiBr solutions of dimethylsulfoxide (DMSO). Interfacial DMSO structure is generally similar to that in-situ, although spectral evidence for an emersion-induced potential shift is observed. The DMSO orientation at Ag electrodes is driven by interaction of the oxygen atom at potentials positive of the potential of zero charge (pzc) and the sulfur atom at potentials negative of the pzc. Pronounced restructuring of DMSO occurs in the vicinity of the pzc. Specific interactions between DMSO and electrolyte ions are clearly detected in the emersed interface. The observed potential shift is attributed to reorientation of the DMSO solvent dipoles at the emersed layer | gas interface. These results represent the first spectroscopic evidence for the existence of an emersion-induced potential shift.
KW - Emersed electrochemical interface
KW - Non-aqueous solutions
KW - Surface enhanced Raman scattering
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U2 - 10.1016/s0022-0728(99)00428-3
DO - 10.1016/s0022-0728(99)00428-3
M3 - Article
AN - SCOPUS:0033358041
VL - 479
SP - 32
EP - 42
JO - Journal of Electroanalytical Chemistry
JF - Journal of Electroanalytical Chemistry
SN - 0022-0728
IS - 1
ER -