Angular dependence of core hole screening in LiCoO2: A DFT+U calculation of the oxygen and cobalt K-edge x-ray absorption spectra

Abstract

Angular-dependent core hole screening effects have been found in the cobalt K-edge x-ray absorption spectrum of LiCoO2, using high-resolution data and parameter-free general gradient approximation plus U calculations. The Co 1s core hole on the absorber causes strong local attraction. The core hole screening on the cobalt nearest-neighbors induces a 2 eV shift in the density of states with respect to the on-site 1s-3d transitions, as detected in the Co K pre-edge spectrum. Our density functional theory plus U calculations reveal that the off-site screening is different in the out-of-plane direction, where a 3 eV shift is visible in both calculations and experiment. The detailed analysis of the inclusion of the core hole potential and the Hubbard parameter U shows that the core hole is essential for the off-site screening while U improves the description of the angular-dependent screening effects. In the case of oxygen K edge, both the core hole potential and the Hubbard parameter improve the relative positions of the spectral features.