Single-particle excitation of core states in epitaxial silicene

Recent studies of core-level x-ray photoelectron spectroscopy (XPS) spectra of silicene on ${\mathrm{ZrB}}₂(0001)$ were found to be inconsistent with the density of states (DOS) of a planar-like structure that has been proposed as the ground state by density functional theory (DFT). To resolve the discrepancy, a reexamination of the XPS spectra and direct theoretical access of accurate single-particle excitation energies are desired. By analyzing the XPS data using symmetric Voigt functions, different binding energies and their sequence of Si $2p$ orbitals can be assigned from previously reported ones where asymmetric pseudo-Voigt functions are adopted. Theoretically, we have adopted an approach developed very recently, which follows the sophisticated $\mathrm{\ensuremath{\Delta}}$ self-consistent field $(\mathrm{\ensuremath{\Delta}}\mathrm{SCF})$ methods, to study the single-particle excitation of core states. In the calculations, each single-particle energy and the renormalized core-hole charge density are calculated straightforwardly via two SCF calculations. By comparing the results, the theoretical core-level absolute binding energies including the splitting due to spin-orbit coupling are in good agreement with the observed high-resolution XPS spectra. The good agreement not only resolves the puzzling discrepancy between experiment and theory (DOS) but also advocates the success of DFT in describing many-body interactions of electrons at the surface.