Temperature-programmed desorption of large molecules: influence of thin film structure and origin of intermolecular repulsion

Although the exact knowledge of the binding energy of organic adsorbates on solid surfaces is of vital importance for the realization of molecular nanostructures and the theoretical modelling of molecule-substrate interactions, an experimental determination is by no means trivial. Temperature-programmed desorption (TPD) is a widely used technique that can provide such information, but a quantitative analysis requires detailed knowledge of the pre-exponential factor of desorption and is therefore rarely performed on a quantitative level for larger molecules that often exhibit notable mutual intermolecular interactions. Here, we provide a thorough anlysis of TPD data of monolayers of pentacene and perfluoropentacene adsorbed on Au(111) that serve as a model system for polycyclic aromatic hydrocarbons adsorbed on noble metal surfaces. We show that the pre-exponential factor varies by several orders of magnitude with the surface coverage and evolves in a step-like fashion due to the sudden activation of a rotational degree of freedom during thermally controlled monolayer desorption. Using complementary coverage-dependent work function measurements, the interface dipole moments were determined. This allows to identify the origin and quantify the relative contributions of the lateral intermolecular interactions, which we modelled by force field calculations. This analysis clearly shows that the main cause for intermolecular repulsion are electrostatic interactions between the intramolecular charge distributions, while interface dipoles play only a minor role.