Electron transport through conjugated molecules

When the π system only tells part of the story

Gemma C. Solomon, David Q. Andrews, Richard P. Van Duyne, Mark A Ratner

Research output: Contribution to journalArticle

78 Citations (Scopus)

Abstract

In molecular transport junctions, current is monitored as a function of the applied voltage for a single molecule assembled between two leads. The transport is modulated by the electronic states of the molecule. For the prototypical delocalized systems, namely, p-conjugated aromatics, the p system usually dominates the transport. Herein, we investigate situations where model calculations including only the p system do not capture all of the subtleties of the transport properties. Including both the s and p contributions to charge transport allows us to demonstrate that while there is generally good agreement, there are discrepancies between the methods. We find that model calculations with only the p system are insufficient where the transport is dominated by quantum interference and cases where geometric changes modulate the coupling between different regions of the p system. We examine two specific molecular test cases to model these geometric changes: the angle dependence of coupling in (firstly) a biphenyl and (secondly) a nitro substituent of a cross-conjugated unit.

Original languageEnglish
Pages (from-to)257-264
Number of pages8
JournalChemPhysChem
Volume10
Issue number1
DOIs
Publication statusPublished - Jan 12 2009

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Molecules
molecules
electrons
Electronic states
Transport properties
Charge transfer
transport properties
interference
Electric potential
electric potential
electronics
Electron Transport
diphenyl

Keywords

  • π systems
  • Conjugation
  • Density functional calculations
  • Electron transport
  • Hückel model

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Electron transport through conjugated molecules : When the π system only tells part of the story. / Solomon, Gemma C.; Andrews, David Q.; Van Duyne, Richard P.; Ratner, Mark A.

In: ChemPhysChem, Vol. 10, No. 1, 12.01.2009, p. 257-264.

Research output: Contribution to journalArticle

Solomon, Gemma C. ; Andrews, David Q. ; Van Duyne, Richard P. ; Ratner, Mark A. / Electron transport through conjugated molecules : When the π system only tells part of the story. In: ChemPhysChem. 2009 ; Vol. 10, No. 1. pp. 257-264.
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