Abstract. We perform Density Functional Theory (DFT) calculations on molecular junctions consisting of a single molecule between two Au(111) electrodes. The molecules consist of an alkane or aryl bridge connecting acceptor, donor, or thiol endgroups in various combinations. The molecular geometries are optimised and wavefunctions and eigenstates of the junction calculated using the DFT method, and then the electron transport properties for the junction are calculated within the Non-Equilibrium Greens Function (NEGF) formalism. The current-voltage or i(V) characteristics for the various molecules are then compared. Rectification is observed for these molecules, particularly for the donor-bridge-acceptor case where the bridge is an alkane, with rectification being in the same direction as the original findings of Aviram and Ratner [1], at least for relatively large negative and positive applied bias. However, at smaller bias rectification is in the opposite direction and is attributed to the lowest unoccupied orbital associated with the acceptor group.Keywords. Molecular electronics, single molecule conductance, electron transport, ab-initio transport calculations, molecular junctions.
IntroductionThe idea that a single molecule can act as a current rectifier dates back to at least 1974. Aviram and Ratner [1] proposed a model for electron transport through a molecule connected to external reservoirs that predicts rectifying behaviour by a certain class of molecules, consisting of donor and acceptor groups separated by an insulating σ-bridge, the so-called DσA molecules. Electrons can tunnel effectively through the σ-barrier from the acceptor to donor groups, once a sufficient bias is applied to allow donation from the cathode to acceptor and donor to anode. Tunneling in the opposite direction however is suppressed, giving the rectifying behaviour.Experimental verification of this idea was slow to follow, due to a lack of tools to probe single-molecule transport. Early attempts [2] were questionable due to the uncertainty in the source of the rectification. Metzger [3] presented further experimental results, where the DσA molecular junction was formed from a Langmuir-Blodgett multi-or monolayer with a second electrode deposited onto the L-B layer. The molecule was γ-(n-hexadecyl)quinolinum tricyanoquinodimethanide Substantial rectifying behaviour for the molecular junction was evident in the results with an asymmetry in the i(V) curve of several orders of magnitude between forward and reverse bias.In the intervening years there has been a wealth of further experimental and computational studies of molecular junctions and many aspects of the problem have been revealed (see, for example, [4][5][6][7] and references therein) such as the importance of the contact regions between molecule and electrode.