Quantum Many-Body Effects in X-Ray Spectra Efficiently Computed using a Basic Graph Algorithm

TL;DR

This paper introduces an efficient, graph-based computational framework for accurately modeling many-electron effects in x-ray spectra, improving interpretation of materials characterization data.

Contribution

It presents a non-diagrammatic, determinant-based approach combined with a breadth-first search algorithm to efficiently compute many-electron processes in x-ray spectra.

Findings

Accurately reproduces experimental x-ray spectra of transition metal oxides.

Demonstrates computational efficiency for extended systems.

Captures many-electron effects beyond traditional methods like Bethe-Salpeter.

Abstract

The growing interest in using x-ray spectroscopy for refined materials characterization calls for accurate electronic-structure theory to interpret x-ray near-edge fine structure. In this work, we propose an efficient and unified framework to describe all the many-electron processes in a Fermi liquid after a sudden perturbation (such as a core hole). This problem has been visited by the Mahan-Nozi\'eres-De Dominicis (MND) theory, but it is intractable to implement various Feynman diagrams within first-principles calculations. Here, we adopt a non-diagrammatic approach and treat all the many-electron processes in the MND theory on an equal footing. Starting from a recently introduced determinant formalism [Phys. Rev. Lett. 118, 096402 (2017)], we exploit the linear-dependence of determinants describing different final states involved in the spectral calculations. An elementary graph algorithm, breadth-first search, can be used to quickly identify the important determinants for shaping the spectrum, which avoids the need to evaluate a great number of vanishingly small terms. This search algorithm is performed over the tree-structure of the many-body expansion, which mimics a path-finding process. We demonstrate that the determinantal approach is computationally inexpensive even for obtaining x-ray spectra of extended systems. Using Kohn-Sham orbitals from two self-consistent fields (ground and core-excited state) as input for constructing the determinants, the calculated x-ray spectra for a number of transition metal oxides are in good agreement with experiments. Many-electron aspects beyond the Bethe-Salpeter equation, as captured by this approach, are also discussed, such as shakeup excitations and many-body wave function overlap considered in Anderson's orthogonality catastrophe.