Resolving molecular frontier orbitals in molecular junctions with kHz resolution

Abstract

Designing and building single-molecule circuits with tailored functionalities requires a detailed knowledge of the junction electronic structure. The energy of frontier molecular orbitals and their electronic coupling with the electrodes play a key role in determining the conductance of nanoscale molecular circuits. Here, we developed a method for measuring the current–voltage (I–V) characteristics of single-molecule junctions with a time resolution that is two orders of magnitude higher than previously achieved. These I–V measurements with high temporal resolution, together with atomistic simulations, enabled us to characterize in detail the frontier molecular states and their evolution in sub-angstrom stretching of the junction. For a series of molecules, changes in the electronic structure were resolved as well as their fluctuations prior to junction breakdown. This study describes a new methodology to determine the key frontier MO parameters at single-molecule junctions and demonstrates how these can be mechanically tuned at the single-molecule level.