Visualizing the orientational dependence of an intermolecular potential

Sweetman, Adam and Rashid, Mohammad A. and Jarvis, Samuel P. and Dunn, Janette L. and Rahe, Philipp and Moriarty, Philip (2016) Visualizing the orientational dependence of an intermolecular potential. Nature Communications, 7. ISSN 2041-1723

Abstract

Scanning probe microscopy can now be used to map the properties of single molecules with intramolecular precision by functionalization of the apex of the scanning probe tip with a single atom or molecule. Here we report on the mapping of the three-dimensional potential between fullerene (C-60) molecules in different relative orientations, with sub-Angstrom resolution, using dynamic force microscopy (DFM). We introduce a visualization method which is capable of directly imaging the variation in equilibrium binding energy of different molecular orientations. We model the interaction using both a simple approach based around analytical Lennard-Jones potentials, and with dispersion-force-corrected density functional theory (DFT), and show that the positional variation in the binding energy between the molecules is dominated by the onset of repulsive interactions. Our modelling suggests that variations in the dispersion interaction are masked by repulsive interactions even at displacements significantly larger than the equilibrium intermolecular separation.