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Journal of the Optical Society of America B

Journal of the Optical Society of America B


  • Editor: Grover Swartzlander
  • Vol. 30, Iss. 1 — Jan. 1, 2013
  • pp: 219–223

Third-order effects in resonant sum-frequency-generation signals at electrified metal/liquid interfaces

Patrick Koelsch, Mutlu I. Muglali, Michael Rohwerder, and Andreas Erbe  »View Author Affiliations

JOSA B, Vol. 30, Issue 1, pp. 219-223 (2013)

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Vibrational sum-frequency-generation (SFG) spectroscopy experiments at electrified interfaces involve incident laser radiation at frequencies in the IR and near-IR/visible regions as well as a static electric field on the surface. Here we show that mixing the three fields present on the surface can result in third-order effects in resonant SFG signals. This was achieved for closed packed self-assembled monolayers (SAMs) with molecular groups of high optical nonlinearity and surface potentials similar to those typically applied in cyclic voltammograms. Broadband SFG spectroscopy was applied to study a hydrophobic well-ordered araliphatic SAM on an Au(111) surface using a thin-layer analysis cell for spectro-electrochemical investigations in a 100 mM NaOH electrolyte solution. Resonant contributions were experimentally separated from nonresonant contributions of the Au substrate and theoretically analyzed using a fitting function including third-order terms. The resulting ratio of third-order to second-order susceptibilities was estimated to be O(1010)m/V.

© 2012 Optical Society of America

OCIS Codes
(190.4350) Nonlinear optics : Nonlinear optics at surfaces
(300.6420) Spectroscopy : Spectroscopy, nonlinear

ToC Category:

Original Manuscript: September 4, 2012
Revised Manuscript: November 21, 2012
Manuscript Accepted: November 21, 2012
Published: December 20, 2012

Patrick Koelsch, Mutlu I. Muglali, Michael Rohwerder, and Andreas Erbe, "Third-order effects in resonant sum-frequency-generation signals at electrified metal/liquid interfaces," J. Opt. Soc. Am. B 30, 219-223 (2013)

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