Lawrence Berkeley National Laboratory

X-ray absorption spectroscopy at the L-edge of 3d transition metals is widely used for probing the valence electronic structure at the metal site via 2p-3d transitions. Assessing the information contained in L-edge absorption spectra requires systematic comparison of experiment and theory. We here investigate the Cr L-edge absorption spectrum of high-spin chromium acetylacetonate Cr^III(acac)₃ in solution. Using a transmission flatjet enables determining absolute absorption cross sections and spectra free from X-ray-induced sample damage. We address the challenges of measuring Cr L absorption edges spectrally close to the O K absorption edge of the solvent. We critically assess how experimental absorption cross sections can be used to extract information on the electronic structure of the studied system by comparing our results of this Cr^III (3d³) complex to our previous work on L-edge absorption cross sections of Mn^III(acac)₃ (3d⁴) and Mn^II(acac)₂ (3d⁵). Considering our experimental uncertainties, the most insightful experimental observable for this d³(Cr^III)-d⁴(Mn^III)-d⁵(Mn^II) series is the L-edge branching ratio, and we discuss it in comparison to semiempirical multiplet theory and ab initio restricted active space calculations. We further discuss and analyze trends in integrated absorption cross sections and correlate the spectral shapes with the local electronic structure at the metal sites.