1-Adamantanethiolate monolayer displacement kinetics follow a universal form

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

Research output: Contribution to journalArticlepeer-review

42 Scopus citations


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
Issue number35
StatePublished - Sep 5 2007

All Science Journal Classification (ASJC) codes

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


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