Nonlinear charge transport in redox molecular junctions: A marcus perspective

Agostino Migliore*, Abraham Nitzan

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Redox molecular junctions are molecular conduction junctions that involve more than one oxidation state of the molecular bridge. This property is derived from the ability of the molecule to transiently localize transmitting electrons, implying relatively weak molecule-leads coupling and, in many cases, the validity of the Marcus theory of electron transfer. Here we study the implications of this property on the nonlinear transport properties of such junctions. We obtain an analytical solution of the integral equations that describe molecular conduction in the Marcus kinetic regime and use it in different physical limits to predict some important features of nonlinear transport in metal-molecule-metal junctions. In particular, conduction, rectification, and negative differential resistance can be obtained in different regimes of interplay between two different conduction channels associated with different localization properties of the excess molecular charge, without specific assumptions about the electronic structure of the molecular bridge. The predicted behaviors show temperature dependences typically observed in the experiment. The validity of the proposed model and ways to test its predictions and implement the implied control strategies are discussed.

Original languageEnglish
Pages (from-to)6669-6685
Number of pages17
JournalACS Nano
Volume5
Issue number8
DOIs
StatePublished - 23 Aug 2011

Keywords

  • Marcus theory
  • NDR
  • electrochemical electron transfer
  • molecular electronics
  • rectification
  • redox molecular junctions

Fingerprint

Dive into the research topics of 'Nonlinear charge transport in redox molecular junctions: A marcus perspective'. Together they form a unique fingerprint.

Cite this