Initial Stages of Oxidation on Graphitic Surfaces: Photoemission Study and Density Functional Theory Calculations

The initial oxidation stages of perfect and defective graphitic surfaces exposed to atomic oxygen have been studied with a combined high-resolution photoemission spectroscopy (HR-PES) and density functional theory (DFT) computational approach. The resulting oxygen-containing surface functional groups are identified by analyzing the multicornponent C 1s and O 1s core level spectra that are then interpreted on the basis of DFF calculations. In the initial oxidation stage, epoxy groups are formed on perfect graphene, whereas the preferential adsorption of the O atoms on the vacancies of the defective surfaces results in structures containing pairs of oxygen atoms in ether and carbonyl (semiquinone) coil figurations. The formation of these functional groups is preceded by metastable structures consisting of single O atoms occupying single C vacancies