TY - JOUR
T1 - Nonlinear charge transport in redox molecular junctions
T2 - A marcus perspective
AU - Migliore, Agostino
AU - Nitzan, Abraham
PY - 2011/8/23
Y1 - 2011/8/23
N2 - 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.
AB - 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.
KW - Marcus theory
KW - NDR
KW - electrochemical electron transfer
KW - molecular electronics
KW - rectification
KW - redox molecular junctions
UR - http://www.scopus.com/inward/record.url?scp=80052068429&partnerID=8YFLogxK
U2 - 10.1021/nn202206e
DO - 10.1021/nn202206e
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AN - SCOPUS:80052068429
SN - 1936-0851
VL - 5
SP - 6669
EP - 6685
JO - ACS Nano
JF - ACS Nano
IS - 8
ER -