Resonant vibrations, peak broadening, and noise in single molecule contacts: the nature of the first conductance peak.

We carry out experiments on single-molecule junctions at low temperatures, using the mechanically controlled break junction technique. Analyzing the results obtained with various molecules, the nature of the first peak in the differential conductance spectra is elucidated. We observe an electronic transition with a vibronic fine structure, if the first peak occurs at small voltages. This regime can accurately be described by the resonant tunneling model. At higher voltages, additional smearing is observed and no fine structure can be resolved. A detailed analysis of the noise signal indicates that the onset of current is associated with strong fluctuations as a precursor of current flow. The data indicate that a complex fluctuation-driven transport mechanism takes over in this regime.