Theoretic Study of Sulfur-Doped Graphdiynes by X‑ray Spectroscopy

Sulfur-doped graphdiyne at different sites has a tremendous impact on its electronic structure and properties. Due to the large number of S-doping sites, there is no comprehensive and systematic experimental and theoretical study regarding the identification of S-doped graphdiyne configurations. In this paper, X-ray photoelectron (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra as well as geometries of 10 sulfur-doped graphdiyne molecules have been simulated at the density functional theory (DFT) level. Different types of carbon spectra were theoretically modeled to analyze the contribution of the spectra. Calculated results show that the NEXAFS spectra exhibit a clear dependence on the local structure. The theoretically simulated XPS spectra are in good agreement with the experimental spectra. The XPS spectra combined with the NEXAFS spectra can provide effective information for identifying the 10 S-doped conformations. Our research results provide further theoretical prediction and guidance for the experimental synthesis of S-doped graphdiyne, which solves the difficult problem of identification of S-doped carbon-based materials.