Organic/metal interfaces in self-assembled monolayers of conjugated thiols: A first-principles benchmark study

Georg Heimel*, Lorenz Romaner, Jean Luc Brédas, Egbert Zojer

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

127 Scopus citations


We present an extensive theoretical study of a self-assembled monolayer of a prototype π-conjugated thiol on Au(1 1 1). A series of experimentally accessible quantities are calculated and compared to available experimental data. After assessing the methodology and re-evaluating experimental data in the light of our theoretical results, we focus on the interfacial phenomena determining the modification of the effective workfunction of the substrate and link our findings to the energetic alignment of the frontier molecular orbitals with the metal Fermi level. Since we find no evidence of charge transfer between metal and molecule, the observed interfacial phenomena are rationalized in terms of charge fluctuations and electrostatics at the atomic length scale. The microscopic picture established in this work provides a deeper understanding of the interfacial processes that govern the working principle of single-molecule electronics and organic electronic devices.

Original languageEnglish (US)
Pages (from-to)4548-4562
Number of pages15
JournalSurface Science
Issue number19
StatePublished - Oct 1 2006
Externally publishedYes


  • Aromatics
  • Density-functional calculations
  • Interface dipole
  • Metal-semiconductor interfaces
  • Molecular electronics
  • Organic molecules
  • Self-assembled
  • Thiols

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Surfaces, Coatings and Films
  • Materials Chemistry


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