A DFT study of halogen atoms adsorbed on graphene layers

Abstract

In this work, ab initio density functional theory calculations were performed in order to study the structural and electronic properties of halogens (X = fluorine, chlorine, bromine or iodine) that were deposited on both sides of graphene single layers (X–graphene). The adsorption of these atoms on only one side of the layer with hydrogen atoms adsorbed on the other was also considered (H,X–graphene). The results indicate that the F–C bond in the F–graphene system causes an sp2 to sp3 transition of the carbon orbitals, and similar effects seem to occur in the H,X–graphene systems. For the other cases, two configurations are found: bonded (B) and non-bonded (NB). For the B configuration, the structural arrangement of the atoms was similar to F–graphene and H–graphene (graphane), although the electronic structures present some differences. In the NB configuration, the interaction between the adsorbed atoms and the graphene layer seems to be essentially of the van der Waals type. In these cases, the original shape of the graphene layer presents only small deviations from the pristine form and the adsorbed atoms reach equilibrium far from the sheet. The F–graphene structure has a direct bandgap of approximately 3.16 eV at the Γ point, which is a value that is close to the value of 3.50 eV that was found for graphane. The Cl–graphene (B configuration), H,F–graphene and H,Cl–graphene systems have smaller bandgap values. All of the other systems present metallic behaviours. Energy calculations indicate the possible stability of these X–graphene layers, although some considerations about the possibility of spontaneous formation have to be taken into account.