Ab initio multiplet plus cumulant approach for correlation effects in x-ray photoelectron spectroscopy

Abstract

The treatment of electronic correlations in open-shell systems is among the most challenging problems of condensed matter theory. Current approximations are only partly successful. Ligand field multiplet theory (LFMT) has been widely successful in describing intra-atomic correlation effects in x-ray spectra, but typically ignores itinerant states. The cumulant expansion for the one electron Greens function has been successful in describing shake-up effects but ignores atomic multiplets. More complete methods, such as dynamic mean-field theory can be computationally problematic. Here we show that separating the dynamic Coulomb interactions into local and longer-range parts with ab initio parameters yields a combined multiplet plus cumulant approach that accounts for both local atomic multiplets and satellite excitations. The approach is illustrated in transition metal oxides and explains the multiplet peaks, charge-transfer satellites and distributed background features observed in XPS experiment.

References in corpus (16)

• Multiplet ligand-field theory using Wannier orbitals
• The valence electron photoemission spectrum of semiconductors: ab initio description of multiple satellites
• Accurate absolute and relative core-level binding energies from $GW$
• Dynamical screening effects in correlated materials: plasmon satellites and spectral weight transfers from a Green's function ansatz to extended dynamical mean field theory
• LDA+DMFT approach to core-level spectroscopy: application to 3d transition metal compounds
• Real time cumulant approach for charge transfer satellites in x-ray photoemission spectra
• Charge-transfer effect in hard x-ray 1$s$ and 2$p$ photoemission spectra: LDA+DMFT and cluster-model analysis
• Equation of motion coupled-cluster approach for intrinsic losses in x-ray spectra
• Particle-hole cumulant approach for inelastic losses in x-ray spectra
• K-edge X-ray absorption spectra in transition metal oxides beyond the single particle approximation: shake-up many body effects
• Real-time coupled-cluster approach for the cumulant Green's function
• Satellite structures in the spectral functions of semiconductor quantum well two-dimensional electron gases: a GW plus cumulant study
• Many-body effects in x-ray absorption and magnetic circular dichroism spectra within the LSDA+DMFT framework
• High pressure evolution of Fe${}_2$O${}_3$ electronic structure revealed by X-ray absorption
• Non-linear response in the cumulant expansion for core hole photoemission
• Web-Based Methods for X-ray and Photoelectron Spectroscopies