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We carry out experiments on single-molecule junctions at low temperatures,using the mechanically controlled break junction technique. Analyzing theresults received with more than ten different molecules the nature of the firstpeak in the differential conductance spectra is elucidated. We observe anelectronic transition with a vibronic fine structure, which is most frequentlysmeared out and forms a broad peak. In the usual parameter range we find strongindications that additionally fluctuations become active even at lowtemperatures. We conclude that the electrical field feeds instabilities, whichare triggered by the onset of current. This is underscored by noisemeasurements that show strong anomalies at the onset of charge transport.

Resonant vibrations, peak broadening and noise in single molecule contacts: beyond the resonant tunnelling picture