Reorganization energy upon charging a single molecule on an insulator measured by atomic force microscopy

Intermolecular single-electron transfer on electrically insulating films is a key process in molecular electronics(1-4) and an important example of a redox reaction(5,6). Electron-transfer rates in molecular systems depend on a few fundamental parameters, such as interadsorbate distance, temperature and, in particular, the Marcus reorganization energy(7). This crucial parameter is the energy gain that results from the distortion of the equilibrium nuclear geometry in the molecule and its environment on charging(8,9). The substrate, especially ionic films(10), can have an important influence on the reorganization energy(11,12). Reorganization energies are measured in electrochemistry(13) as well as with optical(14,15) and photoemission spectroscopies(16,17), but not at the single-molecule limit and nor on insulating surfaces. Atomic force microscopy (AFM), with single-charge sensitivity(18-22), atomic-scale spatial resolution(20) and operable on insulating films, overcomes these challenges. Here, we investigate redox reactions of single naphthalocyanine (NPc) molecules on multilayered NaCl films. Employing the atomic force microscope as an ultralow current meter allows us to measure the differential conductance related to transitions between two charge states in both directions. Thereby, the reorganization energy of NPc on NaCl is determined as (0.8 +/- 0.2) eV, and density functional theory (DFT) calculations provide the atomistic picture of the nuclear relaxations on charging. Our approach presents a route to perform tunnelling spectroscopy of single adsorbates on insulating substrates and provides insight into single-electron intermolecular transport.