Microscopic Theory, Analysis, and Interpretation of Conductance Histograms in Molecular Junctions

Molecular junctions have emerged as a powerful tool to investigate chemistry and physics at the single-molecule limit. However, their utility as a platform to develop spectroscopies and construct molecular devices is limited by the broad conductance histogram typically encountered in experiments. Here we advance a microscopic theory of the conductance histogram by merging the theory of force spectroscopy developed in biophysics with molecular conductance. The theory augments the information content that can be extracted from molecular junction experiments and identifies the key physical elements that need to be controlled to enhance the ability of this class of experiments to resolve molecular events.