Electronic transport properties of single-molecule junctions have been widely measured by several techniques, including mechanically controllable break junctions, electromigration break junctions, and by means of scanning tunneling microscopes. In parallel, many theoretical tools have been developed and refined for describing such transport properties and for obtaining numerical predictions. Most prominent among these theoretical tools are those based upon density functional theory. In this review, theory and experiment are critically compared, and this confrontation leads to several important conclusions. The theoretically predicted trends nowadays reproduce the experimental findings well for series of molecules with a single well-defined control parameter, such as the length of the molecules. The quantitative agreement between theory and experiment usually is less convincing, however. Two main sources for the quantitative discrepancies can be identified. Experimentally, the atomic structure of the junction typically realized in the measurement is not well known, so simulations rely on plausible scenarios. In theory, correlation effects can be included only in approximations that are difficult to control for experimentally relevant situations. Therefore, one typically expects qualitative agreement with present modeling tools; in exceptional cases a quantitative agreement has already been achieved. For further progress, benchmark systems are required that are sufficiently well defined by experiment to allow quantitative testing of the approximation schemes underlying the theoretical modeling. Several key experiments can be identified suggesting that the present description may even be qualitatively incomplete in some cases. Such key experimental observations and their current models are also discussed here, leading to several suggestions for extensions of the models toward including dynamic image charges, electron correlations, and polaron formation.

Since the work of Walter Schottky, it is known that the shot-noise power for a completely uncorrelated set of electrons increases linearly with the time-averaged current. At zero temperature and in the absence of inelastic scattering, the linearity relation between noise power and average current is quite robust, in many cases even for correlated electrons. Through high-bias shot-noise measurements on single Au atom point contacts, we find that the noise power in the high-bias regime shows highly nonlinear behavior even leading to a decrease in shot noise with voltage. We explain this nonlinearity using a model based on quantum interference of electron waves with varying path difference due to scattering from randomly distributed defect sites in the leads, which makes the transmission probability for these electrons both energy and voltage dependent.