Odd-even effects in self-assembled monolayers of ω-(biphenyl-4-yl) alkanethiols: A first-principles study

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

70 Scopus citations


Conjugated molecules with a saturated alkyl linker between a thiol docking group and the π-conjugated core have been shown to form self-assembled monolayers (SAMs) with a high degree of long-range order and uniformity. Additionally, pronounced odd-even effects have been observed in a number of properties characterizing these SAMs. We focus on ω-(biphenyl-4-yl) alkanethiols with n = 0-6-(CH2)n- units deposited on Au(111) and investigate the microscopic origin of these odd-even effects in terms of the local sulfur-gold bonding geometry by employing first-principles calculations. An additional structural parameter, the torsion angle between the two phenyl rings in the biphenyl moiety, is identified and its relation to the experimentally observed odd-even effects is discussed. More importantly, we address relevant quantities for the application of these SAMs in molecular electronic devices, in particular, the modification of the work function of the underlying metal substrate and the energetic alignment of the molecular orbitals in the SAM with the Fermi level. While no clear trend emerges for the former, we find pronounced odd-even effects for the latter. Furthermore, the insertion of a single methylene unit between the biphenyl core and the thiol appears to largely decouple the valence electronic systems of the π-conjugated segment and the gold substrate. Our results thus provide a solid theoretical basis for the interface energetics in this important class of systems.

Original languageEnglish (US)
Pages (from-to)474-482
Number of pages9
Issue number2
StatePublished - Jan 15 2008
Externally publishedYes

ASJC Scopus subject areas

  • General Materials Science
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry


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