The adsorption of polyaromatic hydrocarbons (PAHs) on metallic substrates has been of interest in the field of optoelectronics due to the possibility of designing complex materials with tunable properties through surface functionalization with organic molecules. Much of the modelling research in this field has focused on perfectly symmetrical (idealized) substrates. Limited research has investigated the effect of substrate irregularities, such as adatoms, on the binding of PAHs onto substrates. Here, we examine how the presence of substrate-bound adatoms affects the binding of coronene and hexahelicene monomers and dimers onto Au(111) and Cu(111) substrates using a density functional theory approach. We found that helicene monomers were more effectively able to adapt to the presence of the adatoms than coronene by coiling around the adatoms. Whereas upon adsorption on an ideal (111) surface, coronene can establish significantly stronger dispersive interactions than helicenes, adatom defects reverse the trend. For helicenes, the degree of flattening near the surface and molecular coiling were strongly influenced by the extent of the adatom defect, as a result of the interplay between the molecule’s drive to maximize overlap with the underlying surface and the enhanced reactivity of lower-coordinated adatoms.
MD trajectories and .xyz structures for adsorbed helicene molecules