Intra-atomic many-body effects in p-shell photoelectron spectra of Cr3+ ions -: art. no. 125106

A strict ab initio model of the many-body effects for the free Cr3+ ion is developed in order to provide a benchmark for intra-atomic effects in the XP spectra of Cr3+ compounds. The model contains no empirical fits or assumptions and incorporates all intershell and intrashell couplings and recouplings, relativistic orbitals, spin-orbital coupling, the core hole, and Boltzmann weighted averages for initial state spin-orbit split levels. Synthetic Cr 2p and 3p XP spectra are compared to an experimental spectrum of alpha-Cr2O3. The theory for the free Cr ion accounts for important features of the experimental Cr 2p spectrum, including the spin-orbital splitting energy and the Cr 2p(3/2) doublet. In contrast, the theory only accounts for the grossest features of the experimental Cr 3p spectrum. Comparing experiment with theory highlights the importance of both intra-atomic and inter-atomic effects on the XP spectra of Cr3+ compounds.