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Direct Determinatio...
Direct Determination of Absolute Absorption Cross Sections at the L-Edge of Dilute Mn Complexes in Solution Using a Transmission Flatjet
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- Kubin, Markus (författare)
- Helmholtz Zentrum Berlin Mat & Energie GmbH, Inst Methods & Instrumentat Synchrotron Radiat Re, Berlin, Germany
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- Guo, Meiyuan (författare)
- Uppsala universitet,Teoretisk kemi
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- Ekimova, Maria (författare)
- Max Born Inst Nichtlineare Opt & Kurzzeitspektros, Berlin, Germany
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- Baker, Michael L. (författare)
- Univ Manchester Harwell, Sch Chem, Oxon, England
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- Kroll, Thomas (författare)
- SLAG Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA USA
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- Källman, Erik, PhD (författare)
- Uppsala universitet,Teoretisk kemi
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- Kern, Jan (författare)
- Lawrence Berkeley Natl Lab, Mol Biophys & Integrated Bioimaging Div, Berkeley, CA USA
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- Yachandra, Vittal K. (författare)
- Lawrence Berkeley Natl Lab, Mol Biophys & Integrated Bioimaging Div, Berkeley, CA USA
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- Yano, Junko (författare)
- Lawrence Berkeley Natl Lab, Mol Biophys & Integrated Bioimaging Div, Berkeley, CA USA
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- Nibbering, Erik T. J. (författare)
- Max Born Inst Nichtlineare Opt & Kurzzeitspektros, Berlin, Germany
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- Lundberg, Marcus, 1974- (författare)
- Uppsala universitet,Teoretisk kemi
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- Wernet, Philippe, 1971- (författare)
- Helmholtz Zentrum Berlin Mat & Energie GmbH, Inst Methods & Instrumentat Synchrotron Radiat Re, Berlin, Germany
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(creator_code:org_t)
- 2018-04-10
- 2018
- Engelska.
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Ingår i: Inorganic Chemistry. - : AMER CHEMICAL SOC. - 0020-1669 .- 1520-510X. ; 57:9, s. 5449-5462
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https://europepmc.or...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- The 3d transition metals play a pivotal role in many charge transfer processes in catalysis and biology. X-ray absorption spectroscopy at the L-edge of metal sites probes metal 2p–3d excitations, providing key access to their valence electronic structure, which is crucial for understanding these processes. We report L-edge absorption spectra of MnII(acac)2 and MnIII(acac)3 complexes in solution, utilizing a liquid flatjet for X-ray absorption spectroscopy in transmission mode. With this, we derive absolute absorption cross-sections for the L-edge transitions with peak magnitudes as large as 12 and 9 Mb for MnII(acac)2 and MnIII(acac)3, respectively. We provide insight into the electronic structure with ab initio restricted active space calculations of these L-edge transitions, reproducing the experimental spectra with excellent agreement in terms of shapes, relative energies, and relative intensities for the two complexes. Crystal field multiplet theory is used to assign spectral features in terms of the electronic structure. Comparison to charge transfer multiplet calculations reveals the importance of charge transfer in the core-excited final states. On the basis of our experimental observations, we extrapolate the feasibility of 3d transition metal L-edge absorption spectroscopy using the liquid flatjet approach in probing highly dilute biological solution samples and possible extensions to table-top soft X-ray sources.
Ämnesord
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
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Kubin, Markus
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Guo, Meiyuan
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Ekimova, Maria
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Baker, Michael L ...
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Kroll, Thomas
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Källman, Erik, P ...
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visa fler...
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Kern, Jan
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Yachandra, Vitta ...
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Yano, Junko
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Nibbering, Erik ...
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Lundberg, Marcus ...
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Wernet, Philippe ...
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Inorganic Chemis ...
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Uppsala universitet