Theoretical principles of single-molecule electronics: A chemical and mesoscopic view

Yongqiang Xue*, Mark A. Ratner

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

59 Scopus citations


Exploring the use of individual molecules as active components in electronic devices has been at the forefront of nanoelectronics research in recent years. Compared to semiconductor microelectronics, modeling transport in single-molecule devices is much more difficult due to the necessity of including the effects of the device electronic structure and the interface to the external contacts at the microscopic level. Theoretical formulation of the problem therefore requires integrating the knowledge base in surface science, electronic structure theory, quantum transport, and device modeling into a single unified framework starting from the first principles. In this article, we introduce the theoretical framework for modeling single-molecule electronics and present a simple conceptual picture for interpreting the results of numerical computation. We model the device using a self-consistent matrix Green's function method that combines nonequilibrium Green's function theory of quantum transport with atomic-scale description of the device's electronic structure. We view the single-molecule device as "heterostructures" composed of chemically well-defined atomic groups, and analyze the device characteristics in terms of the charge and potential response of these atomic groups to perturbation induced by the metal-molecule coupling and the applied bias voltage. We demonstrate the power of this approach using as examples devices formed by attaching benzene-based molecules of different size and internal structure to the gold electrodes through sulfur end atoms.

Original languageEnglish (US)
Pages (from-to)911-924
Number of pages14
JournalInternational Journal of Quantum Chemistry
Issue number5 SPEC. ISS.
StatePublished - Apr 20 2005


  • Green's function
  • Mesoscopic physics
  • Molecular electronics
  • Molecular wires
  • Nanotechnology
  • Quantum transport

ASJC Scopus subject areas

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


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