Variable contact gap single-molecule conductance determination for a series of conjugated molecular bridges

It is now becoming clear that the characteristics of the whole junction are important in determining the conductance of single molecules bound between two metal contacts. This paper shows through measurements on a series of seven conjugated molecular bridges that contact separation is an important factor in determining the electrical response of the molecular junction. These data are obtained using the I (t) method developed by Haiss et al since the scanning tunnelling microscope tip to substrate separation can be controlled through choice of the set-point (I(0)) current and calibrated with current-distance curves and knowledge of the terminal to terminal length of the molecular wire. The contact gap separation dependence is interpreted as arising from tilting of these molecules in the junction and this model is underpinned by ab initio transport computations. In this respect we make the general observation that conductance increases rather dramatically at higher tilt angle away from the normal for conformationally rigid molecular wires and that this increase in conductance arises from increased electronic coupling between the molecular bridge and the gold contacts.