A surface-adsorbed molecule is contacted with the tip of a scanning tunneling microscope (STM) at a predefined atom. On tip retraction, the molecule is peeled off the surface. During this experiment, a two-dimensional differential conductance map is measured on the plane spanned by the bias voltage and the tip-surface distance. The conductance map demonstrates that tip retraction leads to mechanical gating of the molecular wire in the STM junction. The experiments are compared with a detailed ab initio simulation. We find that density functional theory (DFT) in the local density approximation (LDA) describes the tip-molecule contact formation and the geometry of the molecular junction throughout the peeling process with predictive power. However, a DFT-LDA-based transport simulation following the nonequilibrium Green's function (NEGF) formalism fails to describe the behavior of the differential conductance as found in experiment. Further analysis reveals that this failure is due to the mean-field description of electron correlation in the local density approximation. The results presented here are expected to be of general validity and show that, for a wide range of common wire configurations, simulations which go beyond the mean-field level are required to accurately describe current conduction through molecules. Finally, the results of the present study illustrate that well-controlled experiments and concurrent ab initio transport simulations that systematically sample a large configuration space of molecule-electrode couplings allow the unambiguous identification of correlation signatures in experiment.

A broadly observed phenomenon in experiments on molecular junctions is time dependent switching of the tunneling current[1-5]. In many cases such behavior involves different current states which are attributed to the transfer of single atoms or functional groups in a molecule between different stable configurations. We describe here the investigation of the current switching observed in a molecular junction formed by a PTCDA molecule between an STM tip and an Ag(111) surface, which is believed to be due to the carboxylic oxygen atom switching between the surface and the tip[6]. We use a generalized version of a model developed in 1997 by Gao et al.[7] to investigate the results observed in these experiments. The distribution of the switching events measured in the experiments shows a power law dependence for small positive bias voltages, whereas for negative voltages it shows a constant behavior. Compared to Gao's model, which can only describe the rapid increase of the switching events at a certain onset voltage, our extended model can be used to characterize the whole distribution relating the different behavior to the changes in the potential by the applied bias.