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Electronic Structure of Nitrogen-Doped Graphene in the Ground and Core-Excited States from First-Principles Simulations

MetadataDetails
Publication Date2015-06-23
JournalThe Journal of Physical Chemistry C
AuthorsXin Li, Weijie Hua, Jinghua Guo, Yi Luo
InstitutionsLawrence Berkeley National Laboratory, KTH Royal Institute of Technology
Citations40

We have calculated the N 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of nitrogen-doped monolayer graphene (NG) using density functional theory (DFT) with the equivalent core hole approximation. The hexavacancy (6V) defect and its dependence on the nitrogen-doping concentration have been analyzed in detail via both N 1s → Ļ€* and N 1s → σ* transitions. The NEXAFS spectra are sensitive to the doping concentration of N in the Ļ€* region: diluted doping weakens the main Ļ€* peak and smears the oscillations in this region. The vacancy defect leads to a red-shift in both the Ļ€ and σ spectra. A pyridinic nitrogen at the 6V defect center exhibits a sharp Ļ€* peak at 398.4 eV, which agrees well with the experimental pre-edge structure at 398.6 eV. The σ* peak is split in two, which can serve as the fingerprint to reveal the nature of the defect. A structural change from pyridinic to pyrrolic NG results in a distinctive difference in the spectral shape. The ground-state band structure has also been simulated at the DFT level with periodic boundary conditions. Similar profiles are found in the N 2p projected density of states above the Fermi level and in the N 1s NEXAFS spectra.