Electronic and vibrational properties of graphene monolayers with iron adatoms: A density functional theory study

Periodic density functional calculations on graphene monolayers with and without an iron adatom have been used to elucidate iron-graphene adsorption and its effects on graphene electronic and vibrational properties. Density-of-states calculations and charge density contour plots reveal charge transfer from the iron s orbitals to the d orbitals, in agreement with past reports. Adsorbed iron atoms covalently bind to the graphene substrate, verified by the strong hybridization of iron d-states with the graphene bands in the energy region just below the Fermi level. This adsorption is weak and compared to the well-analyzed CO adsorption on Pt: It is indicated by its small adsorption energy and the minimal change of the substrate geometry due to the presence of the iron adatoms. Graphene vibrational spectra are analyzed though asystematic variation of the graphene supercell size. The shifts of graphene most prominent infrared active vibrational modes due to iron adsorption are explored using normal mode eigenvectors. (C) 2014 Elsevier B.V. All rights reserved.