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 GGA+U calculations. The Co 1s core-hole on the absorber causes strong local attraction. The core-hole screening on the nearest neighbours cobalt 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 DFT+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.

References in corpus (6)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• A linear response approach to the calculation of the effective interaction parameters in the LDA+U method
• First-principles prediction of redox potentials in transition-metal compounds with LDA+U
• Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach
• X-ray Linear Dichroism in cubic compounds: the case of Cr3+ in MgAl2O4
• Site symmetry and crystal symmetry: a spherical tensor analysis

Cited by in corpus (9)

• Theory of proximity-induced exchange coupling in graphene on hBN/(Co, Ni)
• Projector augmented wave calculation of x-ray absorption spectra at the L2,3 edges
• Accurate X-Ray Absorption Predictions for Transition Metal Oxides: An Advanced Self-Consistent-Field Approach Inspired by Many-Body Perturbation Theory
• Hard x-ray emission spectroscopy: a powerful tool for the characterization of magnetic semiconductors
• Successes and failures of Hubbard-corrected density functional theory: The case of Mg doped LiCoO${}_2$
• Role of intercalated Cobalt in the electronic structure of Co${}_{1/3}$NbS${}_2$
• Electronic transport and magnetism in the alternating stack of metallic and highly frustrated magnetic layers in Co${}_{1/3}$NbS${}_2$
• Taming Convergence in the Determinant Approach for X-Ray Excitation Spectra
• Layer-Resolved Many-Electron Interactions in Delafossite PdCoO2 from Standing-Wave Photoemission Spectroscopy