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  High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory

Lima, F. A., Bjornsson, R., Weyhermüller, T., Chandrasekaran, P., Glatzel, P., Neese, F., et al. (2013). High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory. Physical Chemistry Chemical Physics, 15(48), 20911-20920. doi:10.1039/C3CP53133C.

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 Creators:
Lima, Frederico A.1, Author           
Bjornsson, Ragnar1, Author           
Weyhermüller, Thomas1, Author           
Chandrasekaran, Perumalreddy2, Author
Glatzel, Pieter3, Author
Neese, Frank1, Author           
DeBeer, Serena1, 4, Author           
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Department of Chemistry and Biochemistry, Lamar University, Beaumont, TX 77710, USA, ou_persistent22              
3European Synchrotron Radiation Facility , 6 Rue Jules Horowitz, 38043 Grenoble Cedex, France , ou_persistent22              
4Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, USA, ou_persistent22              

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 Abstract: X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core–hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas–Kroll–Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.

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Language(s): eng - English
 Dates: 2013-07-252013-11-072013-12-28
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C3CP53133C
 Degree: -

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Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
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Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: - Volume / Issue: 15 (48) Sequence Number: - Start / End Page: 20911 - 20920 Identifier: ISSN: 1463-9076
CoNE: https://pure.mpg.de/cone/journals/resource/954925272413_1