Electron conduction in molecular wires. I. A scattering formalism

• Published in: The Journal of chemical physics 1994-10, Vol.101 (8), p.6849-6855
• Main Authors: Mujica, V., Kemp, M., Ratner, M. A.
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.468314

We extend a model originally intended for the description of the scanning tunneling microscope (STM) current in molecular imaging of one-dimensional systems, to encompass the more general process of electron transfer between two reservoirs of states. In the STM problem, the reservoirs are naturally associated with the metal density of states of the electrodes. In the molecular electron transfer problem, the identification of the reservoirs with the Franck–Condon weighted density of vibrational states allows a number of fruitful connections with the theory of nonadiabatic electron transfer (ET) in molecules to be established. In this article, we present an exact procedure, based on Löwdin’s partitioning technique, to determine the Green’s function and the T matrix, relevant to the transport process. We obtain compact expressions for the conductance and the density of states in the limit of small applied voltage and low temperature, and discuss the important case where the molecular wire is described by a tight-binding Hamiltonian. Finally, we discuss some physical implications of the model.