1-Adamantanethiolate monolayer displacement kinetics follow a universal form

Héctor M. Saavedra, Corina M. Barbu, Arrelaine A. Dameron, Thomas J. Mullen, Vincent Henry Crespi, Paul S. Weiss

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

Alkanethiol molecules in solution displace 1-adamantanethiolate self-assembled monolayers on Au{111}, ultimately leading to complete molecular exchange. Specifically, here, fast insertion of n-dodecanethiolate at defects in the original 1-adamantanethiolate monolayer nucleates an island growth phase, which is followed by slow ordering of the n-dodecanethiolate domains into a denser and more crystalline form. Langmuir-based kinetics, which describe alkanethiolate adsorption on bare Au{111}, fail to model this displacement reaction. Instead, a Johnson-Mehl-Avrami-Kolmogorov model of perimeter-dependent island growth yields good agreement with kinetic data obtained by Fourier transform infrared spectrometry over 100-fold variation in n-dodecanethiol concentration. Rescaling the growth rate at each concentration collapses all the data onto a single universal curve, suggesting that displacement is a scale-free process. The rate of displacement varies as the square-root of the n-dodecanethiol concentration across the 0.01-1.0 mM range studied.

Original languageEnglish (US)
Pages (from-to)10741-10746
Number of pages6
JournalJournal of the American Chemical Society
Volume129
Issue number35
DOIs
StatePublished - Sep 5 2007

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Monolayers
Islands
Kinetics
Self assembled monolayers
Growth
Spectrometry
Fourier transforms
Fourier Analysis
Crystalline materials
Infrared radiation
Adsorption
Defects
Molecules
Spectrum Analysis

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Saavedra, H. M., Barbu, C. M., Dameron, A. A., Mullen, T. J., Crespi, V. H., & Weiss, P. S. (2007). 1-Adamantanethiolate monolayer displacement kinetics follow a universal form. Journal of the American Chemical Society, 129(35), 10741-10746. https://doi.org/10.1021/ja071116z
Saavedra, Héctor M. ; Barbu, Corina M. ; Dameron, Arrelaine A. ; Mullen, Thomas J. ; Crespi, Vincent Henry ; Weiss, Paul S. / 1-Adamantanethiolate monolayer displacement kinetics follow a universal form. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 35. pp. 10741-10746.
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Saavedra, HM, Barbu, CM, Dameron, AA, Mullen, TJ, Crespi, VH & Weiss, PS 2007, '1-Adamantanethiolate monolayer displacement kinetics follow a universal form', Journal of the American Chemical Society, vol. 129, no. 35, pp. 10741-10746. https://doi.org/10.1021/ja071116z

1-Adamantanethiolate monolayer displacement kinetics follow a universal form. / Saavedra, Héctor M.; Barbu, Corina M.; Dameron, Arrelaine A.; Mullen, Thomas J.; Crespi, Vincent Henry; Weiss, Paul S.

In: Journal of the American Chemical Society, Vol. 129, No. 35, 05.09.2007, p. 10741-10746.

Research output: Contribution to journalArticle

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