Influence of conformation on conductance of biphenyl-dithiol single-molecule contacts

Nano Lett. 2010 Jan;10(1):156-63. doi: 10.1021/nl903084b.

Abstract

The conductance of a family of biphenyl-dithiol derivatives with conformationally fixed torsion angle was measured using the scanning tunneling microscopy (STM)-break-junction method. We found that it depends on the torsion angle phi between two phenyl rings; twisting the biphenyl system from flat (phi = 0 degrees ) to perpendicular (phi = 90 degrees ) decreased the conductance by a factor of 30. Detailed calculations of transport based on density functional theory and a two level model (TLM) support the experimentally obtained cos(2) phi correlation between the junction conductance G and the torsion angle phi. The TLM describes the pair of hybridizing highest occupied molecular orbital (HOMO) states on the phenyl rings and illustrates that the pi-pi coupling dominates the transport under "off-resonance" conditions where the HOMO levels are well separated from the Femi energy.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biphenyl Compounds / chemistry*
  • Chemistry, Organic / methods
  • Crystallization
  • Electric Conductivity
  • Electrochemistry / methods
  • Metals / chemistry
  • Microscopy, Scanning Tunneling / methods
  • Models, Chemical
  • Molecular Conformation
  • Molecular Structure
  • Nanostructures
  • Nanotechnology / methods
  • Quantum Theory
  • Toluene / analogs & derivatives*
  • Toluene / chemistry

Substances

  • Biphenyl Compounds
  • Metals
  • diphenyl
  • Toluene
  • dithiol