Cr L-Edge X-ray Absorption Spectroscopy of CrIII(acac)3 in Solution with Measured and Calculated Absolute Absorption Cross Sections

Kubin, Markus; Guo, Meiyuan; Ekimova, Maria; Källman, Erik; Kern, Jan; Yachandra, Vittal K.; Yano, Junko; Nibbering, Erik T.  J.; Lundberg, Marcus; Wernet, Philippe

doi:10.1021/acs.jpcb.8b04190

Title: Cr L-Edge X-ray Absorption Spectroscopy of Cr^III(acac)₃ in Solution with Measured and Calculated Absolute Absorption Cross Sections

Journal Article · Fri Jun 29 00:00:00 EDT 2018 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.8b04190· OSTI ID:1477344

^[1]; Guo, Meiyuan ^[2]; Ekimova, Maria ^[3]; Källman, Erik ^[2]; Kern, Jan ^[4]; Yachandra, Vittal K. ^[4];

^[4];

^[3];

^[2];

^[1]

Helmholtz Center for Materials and Energy (HZB), Berlin (Germany). Inst. for Methods and Instrumentation for Synchrotron Radiation Research
Uppsala Univ. (Sweden). Dept. of Chemistry. Ångström Lab.
Max Born Inst. for Nonlinear Optics and Short Pulse Spectroscopy, Berlin (Germany)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division

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 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. Finally, 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.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Inst. of Health (NIH) (United States); Human Frontier Science Program (HFSP); Swedish Research Council (SRC); Knut and Alice Wallenberg Foundation (Sweden); German Research Foundation (DFG)

Grant/Contract Number:: AC02-05CH11231; GM110501; GM126289; GM55302; RGP0063/2013; KAW-2013.0020; DFG-NI 492/11-1

OSTI ID:: 1477344

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 122, Issue 29; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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Title: Cr L-Edge X-ray Absorption Spectroscopy of Cr^III(acac)₃ in Solution with Measured and Calculated Absolute Absorption Cross Sections