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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents

ID: 682081.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory
Authors:Lima, Frederico A.; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena
Date of Publication (YYYY-MM-DD):2013
Title of Journal:Physical Chemistry Chemical Physics
Journal Abbrev.:Phys. Chem. Chem. Phys.
Issue / Number:48
Start Page:20911
End Page:20920
Review Status:Peer-review
Audience:Experts Only
Abstract / Description: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 HERFDXAS to complex catalytic systems.
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:Chandrasekaran, P.;Lamar Univ, Dept Chem & Biochem, Beaumont, TX 77710 USA.
Glatzel, P.; European Synchrotron Radiat Facil, F-38043 Grenoble, France.
Identifiers:ISI:000327467000015 [ID No:1]
ISSN:1463-9076 [ID No:2]
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