Adsorption of Lanthanide Atoms on a Graphene Cluster Model Incorporating Stone–Wales Defect

To study the adsorption of lanthanide (Ln) atoms on graphene containing a Stone–Wales defect, we used a cluster model (SWG) and performed calculations at the PBE-D2/DNP level of the density functional theory. Our previous study, where the above combination was complemented with the ECP pseudopotentials, was only partially successful due to the impossibility of calculating terbium-containing systems and a serious error found for the SWG complex with dysprosium. In the present study we employed the DSPP pseudopotentials and completely eliminated the latter two failures. We analyzed the optimized geometries of the full series of fifteen SWG + Ln complexes, along with their formation energies and electronic parameters, such as frontier orbital energies, atomic charges, and spins. In many regards, the two series of calculations show qualitatively similar features, such as roughly M-shaped curves of the adsorption energies and trends in the changes in charge and spin of the adsorbed Ln atoms, as well as the spin density plots. However, the quantitative results can differ significantly. For most characteristics we found no evident correlation with the lanthanide contraction. The only dataset where this phenomenon apparently manifests itself (albeit to a limited and irregular degree) is the changes in the closest Ln…C approaches.