Structure and Binding of Alkanethiolates on Gold and Silver Surfaces: Implications for Self-Assembled Monolayers

Harrell Sellers, Abraham Ulman, Yitzhak Shnidman, James E. Eilers

Research output: Contribution to journalArticle


We performed ab initio geometry optimization of HS and CH3S on cluster models of Au(111), Au(100), Ag(111), and Ag(100) surfaces, at the RECP Hartree-Fock + electron correlation (MBPT2) level. From these we determined classical force field parameters, thus opening the possibility for realistic molecular dynamics (MD) simulations of self-assembled alkanethiolate monolayers on gold and silver surfaces. We find that there are two chemisorption modes, very close in energy, for thiolates on Au(111) surfaces. In the first, the surface-S-C bond angle is ~ 180° (sp hybridization), while in the second it is ~104° (sp3 hybridization). This suggests a possible mechanism for the annealing of alkanethiolate monolayers. We present herein the first molecular mechanics energy minimization using these new force field parameters. Self-assembled monolayers of alkanethiolates on gold and silver are different. The ab initio calculations presented here provide the fundamental understanding of the chemisorption of alkanethiolates on gold and silver surfaces, the surface-adsorbates bonds, and the structure of the monolayers thus formed.

Original languageEnglish (US)
Pages (from-to)9389-9401
Number of pages13
JournalJournal of the American Chemical Society
Issue number21
StatePublished - Oct 1 1993


ASJC Scopus subject areas

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

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