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Adsorption properties of two cationic surfactant classes on silver surfaces studied by means of SERS spectroscopy and ab initio calculations

  • Amphiphiles at Electrode Surfaces
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Amphiphiles at Interfaces

Part of the book series: Progress in Colloid & Polymer Science ((PROGCOLLOID,volume 103))

Abstract

Surface-enhanced Raman microprobe spectroscopy (microSERS) and near-infrared Fourier transform SERS spectroscopy (NIRFT-SERS) are used to study, in situ, the adsorption process of alkylpyridinium bromide (CnPyBr) and alkyltrimethylammonium bromide (CnTAB) adsorbed on charged silver nanoparticle surfaces. Vibrational assignment was achieved by comparison of observed band position and intensity in the Raman spectra with wave numbers and intensities from ab initio LCAOMO-SCF Hartree-Fock calculations at the 6-31G* level.

Information on the monolayer adsorption geometry at the charged surface was obtained on the basis of this assignment. The hydrocarbon tail length was varied from C1 to Cg and the chain vibrations were calculated at different conformational defects (from all tans (ttttt) to all gauche (ggggg)). The adsorption behaviour was investigated as a function of surfactant concentration and alkyl chain length.

The results from of ab initio calculations, alkyl chain length dependence, and the short-range effect of SERS suggest that the CnPB surfactant molecules are adsorbed with the ionic headgroup towards the charged surface and the hydrophobic tail is directed away from the surface. In contrast, the C n TAB surfactants are adsorbed with the headgroup pointing to the surface and the hydrocarbon chain is with the tail running parallel to the surface. An experimental model based on headgroup model compounds was performed to reproduce the SERS spectra corresponding to both kind of surfactants.

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Authors and Affiliations

  1. Institute of Applied Physical Chemistry, Research Center Juelich, 52425, Juelich, Germany

    Dr. A. Tarazona, S. Kreisig, E. Koglin & M. J. Schwuger

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  1. Dr. A. Tarazona
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  2. S. Kreisig
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  3. E. Koglin
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  4. M. J. Schwuger
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J. Texter

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© 1997 Steinkopff-Verlag

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Tarazona, A., Kreisig, S., Koglin, E., Schwuger, M.J. (1997). Adsorption properties of two cationic surfactant classes on silver surfaces studied by means of SERS spectroscopy and ab initio calculations. In: Texter, J. (eds) Amphiphiles at Interfaces. Progress in Colloid & Polymer Science, vol 103. Steinkopff. https://doi.org/10.1007/3-798-51084-9_21

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  • DOI: https://doi.org/10.1007/3-798-51084-9_21

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  • Publisher Name: Steinkopff

  • Print ISBN: 978-3-7985-1084-5

  • Online ISBN: 978-3-7985-1662-5

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