Accurate X-Ray Absorption Predictions for Transition Metal Oxides: An Advanced Self-Consistent-Field Approach Inspired by Many-Body Perturbation Theory

Abstract

Constrained-occupancy self-consistent-field ($Δ$SCF) methods and many-body perturbation theories (MBPT) are two strategies for obtaining electronic excitations from first-principles. Using the two distinct approaches, we study the O $1s$ core excitations that have become increasingly important for characterizing transition metal oxides and developing theory of strong correlations. Interestingly, we find that the $Δ$SCF approach, in its current single-particle form, systematically underestimates the pre-edge intensity for chosen oxides, despite its success in weakly correlated systems. By contrast, the Bethe-Salpeter equation within MBPT predicts much better lineshapes. This inspires us to reexamine the many-electron dynamics of X-ray excitations. We find that the single-particle $Δ$SCF approach can be rectified by explicitly calculating many-body transition amplitudes, producing X-ray spectra in excellent agreement with experiments. Our study paves the way to accurately predict X-ray near-edge spectral fingerprints for physics and materials science beyond the Bethe-Salpether equation.