Clusters binding to the graphene moiré on Ir(111): X-ray photoemission compared to density functional calculations

Abstract

Our understanding of metal-atom cluster adsorption on graphene on Ir(111) is based on elementary chemical ideas, rehybridization, and buckling, supported by density functional theory (DFT) calculations. We tested the DFT picture by comparing calculated core level spectra to x-ray photoemission spectroscopy (XPS) measurements. For pristine graphene, which forms a gently undulating moir\'e on Ir(111), DFT predicts a 140 meV modulation of C $1s$ core level shifts (CLS), consistent with the measured spectrum. With Pt clusters adsorbed, measured Pt $4f$ CLS of the adsorbed clusters also support the calculations. The modulation of the C $1s$ spectrum is strengthened with clusters adsorbed, and C-atom ionization potentials under and in the vicinity of the Pt clusters are shifted enough to be experimentally distinguished as a broad shoulder of positive C $1s$ CLSs. Furthermore, DFT calculations imply that $s{p}^{2}$ to $s{p}^{3}$ graphene rehybridization of C atoms below the Pt cluster induces a 1.1 eV CLS splitting between Pt- and Ir-bonded C atoms; this prediction is also consistent with the XPS data.