We report on angle-resolved photoemission studies of the electronic $\pi$ states of high-quality epitaxial graphene layers on a Ni(111) surface. In this system the electron binding energy of the $\pi$ states shows a strong dependence on the magnetization reversal of the Ni film. The observed extraordinarily large energy shift up to 225 meV of the graphene-derived $\pi$ band peak position for opposite magnetization directions is attributed to a manifestation of the Rashba interaction between spin-polarized electrons in the $\pi$ band and the large effective electric field at the graphene/Ni interface. Our findings show that an electron spin in the graphene layer can be manipulated in a controlled way and have important implications for graphene-based spintronic devices.

The spin-dependent electronic structure of thin epitaxial films of magnetite, ${\mathrm{Fe}}_3{\mathrm{O}}_4\mathrm{}\left(111\right),$ has been investigated at room temperature by means of spin-, energy-, and angle-resolved photoemission spectroscopy. Near the Fermi energy $E_F$ a spin polarization of $-(80\mathrm{}\pm 5)\%$ is found. The spin-resolved photoemission spectra for binding energies between 1.5 eV and $E_F$ show good agreement with spin-split band energies from density-functional calculations.

In situ prepared ${\mathrm{Fe}}_3{\mathrm{O}}_4\left(100\right)$ thin films were studied by means of scanning tunneling microscopy (STM) and spin-polarized photoelectron spectroscopy (SP-PES). The atomically resolved $(\sqrt{2}\times \sqrt{2})R45°$ wavelike surface atomic structure observed by STM is explained based on density functional theory (DFT) and ab initio atomistic thermodynamics calculations as a laterally distorted surface layer containing octahedral iron and oxygen, referred to as a modified $B$ layer. The work-function value of the ${\mathrm{Fe}}_3{\mathrm{O}}_4\left(100\right)$ surface extracted from the cutoff of the photoelectron spectra is in good agreement with that predicted from DFT. On the ${\mathrm{Fe}}_3{\mathrm{O}}_4\left(100\right)$ surface both the SP-PES measurements and the DFT results show a strong reduction of the spin polarization at the Fermi level $\left(E_F\right)$ compared to the bulk density of states. The nature of the states in the majority band gap of the ${\mathrm{Fe}}_3{\mathrm{O}}_4$ surface layer is analyzed.

The electronic structure of the zero-gap two-dimensional graphene has a charge neutrality point exactly at the Fermi level that limits the practical application of this material. There are several ways to modify the Fermi-level-region of graphene, e.g. adsorption of graphene on different substrates or different molecules on its surface. In all cases the so-called dispersion or van der Waals interactions can play a crucial role in the mechanism, which describes the modification of electronic structure of graphene. The adsorption of water on graphene is not very accurately reproduced in the standard density functional theory (DFT) calculations and highly-accurate quantum-chemical treatments are required. A possibility to apply wavefunction-based methods to extended systems is the use of local correlation schemes. The adsorption energies obtained in the present work by means of CCSD(T) are much higher in magnitude than the values calculated with standard DFT functional although they agree that physisorption is observed. The obtained results are compared with the values available in the literature for binding of water on the graphene-like substrates.

We report an element-specific investigation of electronic and magnetic properties of the graphene/Ni(111) system. Using x-ray magnetic circular dichroism, the occurrence of an induced magnetism of the carbon atoms in the graphene layer is observed. We attribute this magnetic moment to the strong hybridization between $\text{C}\pi$ and $\text{Ni}3d$ valence band states. The net magnetic moment of carbon in the graphene layer is estimated to be in the range of $0.05–0.1{\mu }_{\text{B}}$ per atom.

The present manuscript summarizes the modern view on the problem of the graphene–metal interaction. Presently, the close-packed surfaces of d metals are used as templates for the preparation of highly-ordered graphene layers. Different classifications can be introduced for these systems: graphene on lattice-matched and graphene on lattice-mismatched surfaces where the interaction with the metallic substrate can be either “strong” or “weak”. Here these classifications, with the focus on the specific features in the electronic structure in all cases, are considered on the basis of large amount of experimental and theoretical data, summarized and discussed. The perspectives of the graphene–metal interfaces in fundamental and applied physics and chemistry are pointed out.