Finite lifetime broadening of calculated x-ray absorption spectra: possible artefacts close to the edge

TL;DR

This paper examines how different broadening methods affect calculated X-ray absorption spectra near the absorption edge, highlighting potential artefacts and emphasizing careful application for accurate results.

Contribution

It demonstrates that broadening methods are equivalent only above certain energies and warns of artefacts near the edge, especially in complex dichroic spectra.

Findings

Broadening methods are equivalent above a few core level widths.

Near the edge, spurious features can appear with excessive broadening.

Special care is needed for dichroic spectra with multiple core levels.

Abstract

X-ray absorption spectra calculated within an effective one-electron approach have to be broadened to account for the finite lifetime of the core hole. For Green's function based methods this can be achieved either by adding a small imaginary part to the energy or by convoluting the spectra on the real axis with a Lorentzian. We demonstrate on the case of Fe K and L2,3 spectra that these procedures lead to identical results only for energies higher than few core level widths above the absorption edge. For energies close to the edge, spurious spectral features may appear if too much weight is put on broadening via the imaginary energy component. Special care should be taken for dichroic spectra at edges which comprise several exchange-split core levels, such as the L3 edge of 3d transition metals.