An implementation of core level spectroscopies in a real space Projector Augmented Wave density functional theory code

We describe the implementation of K-shell core level spectroscopies (X-ray absorption (XAS), X-ray emission (XES), and X-ray photoemission (XPS)) in the real-space-grid-based Projector Augmented Wave (PAW) GPAW code. The implementation for XAS is based on the Haydock recursion method avoiding computation of unoccupied states. The absolute energy scale is computed with the Delta Kohn–Sham method which is possible using specific PAW setups for the core-hole states. We show computed spectra for selected test cases (gas phase H2O and bulk diamond) and discuss the dependence on grid spacing and box size. In the case of diamond we include vibrational effects by sampling spectra from the ground state vibrational distribution and discuss the importance of those effects for the experimentally observed features. We apply the method to XPS, XES and XAS of CO adsorbed on Ni(100) and compare to experimental data where possible.