Core level binding energies in solids from first-principles

TL;DR

This paper introduces a first-principles method to accurately calculate absolute core level binding energies in solids, accounting for multiplet splittings and avoiding supercell interaction errors.

Contribution

The authors develop a novel approach combining a penalty functional and Coulomb cutoff in density functional theory to improve core level energy calculations.

Findings

Achieved mean absolute error of 0.4 eV compared to experimental data.

Successfully modeled multiplet splittings due to chemical shifts and spin-orbit coupling.

Validated method on eight different metal and insulator cases.

Abstract

A general method is presented to calculate absolute binding energies of core levels in metals and insulators, based on a penalty functional and an exact Coulomb cutoff method in a framework of the density functional theory. The spurious interaction of core holes between supercells is avoided by the exact Coulomb cutoff method, while the variational penalty functional enables us to treat multiplet splittings due to chemical shift, spin-orbit coupling, and exchange interaction on equal footing, both of which are not accessible by previous methods. It is demonstrated that the absolute binding energies of core levels for both metals and insulators are calculated by the proposed method in a mean absolute (percentage) error of 0.4 eV (0.16~\%) for eight cases compared to experimental values measured with X-ray photoemission spectroscopy within a generalized gradient approximation to the exchange-correlation functional.