N. Pauly, S. Tougaard, F. Yubero
Surface Science, 620 (2014) 17-22
doi: 10.1016/j.susc.2013.10.009

The shape and intensity of photoelectron peaks are strongly affected by extrinsic excitations due to electron transport out of the surface (including bulk and surface effects) and to intrinsic excitations due to the sudden creation of the static core hole. These effects must be included in the theoretical description of the emitted photoelectron spectra. We have calculated the effective energy-differential inelastic electron scattering cross section for XPS, including both surface and core hole effects, within the dielectric response theory by means of the QUEELS-XPS software (QUantitative analysis of Electron Energy Losses at Surfaces for XPS). The full XPS spectrum is then modeled by convoluting this energy loss cross section with the primary excitation spectrum that accounts for all effects which are part of the initial photo-excitation process, i.e. lifetime broadening, spin–orbit coupling, and multiplet splitting. The shape of this primary excitation spectrum is determined by requiring close agreement between the resulting theoretical spectrum and the experimental XPS spectrum. These calculations were performed for Cu 2p peaks of Cu, Cu₂O, and CuO. For CuO, we compare the obtained primary excitation spectra with first principle calculations performed with the CTM4XAS software (Charge Transfer Multiplet program for X-ray Absorption Spectroscopy) for the corresponding emissions and we find good quantitative agreement.