Electron transmission through molecules and molecular interfaces

Electron transmission through molecules and molecular interfaces has been a subject of intensive research due to recent interest in electron-transfer phenomena underlying the operation of the scanning-tunneling microscope on one hand, and in the transmission properties of molecular bridges between conducting leads on the other. In these processes, the traditional molecular view of electron transfer between donor and acceptor species gives rise to a novel view of the molecule as a current-carrying conductor, and observables such as electron-transfer rates and yields are replaced by the conductivities, or more generally by current-voltage relationships, in molecular junctions. Such investigations of electrical junctions, in which single molecules or small molecular assemblies operate as conductors, constitute a major part of the active field of molecular electronics. In this article I review the current knowledge and understanding of this field, with particular emphasis on theoretical issues. Different approaches to computing the conduction properties of molecules and molecular assemblies are reviewed, and the relationships between them are discussed. Following a detailed discussion of static-junctions models, a review of our current understanding of the role played by inelastic processes, dephasing and thermal-relaxation effects is provided. The most important molecular environment for electron transfer and transmission is water, and our current theoretical understanding of electron transmission through water layers is reviewed. Finally, a brief discussion of overbarrier transmission, exemplified by photoemission through adsorbed molecular layers or low-energy electron transmission through such layers, is provided. Similarities and differences between the different systems studied are discussed.