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  Comparison of multireference ab initio wavefunction methodologies for X- ray absorption edges: A case study on [Fe(II/III)Cl4]2-/1- molecules

Maganas, D., Kowalska, J. K., Nooijen, M., DeBeer, S., & Neese, F. (2019). Comparison of multireference ab initio wavefunction methodologies for X- ray absorption edges: A case study on [Fe(II/III)Cl4]2-/1- molecules. The Journal of Chemical Physics, 150(10): 104106. doi:10.1063/1.5051613.

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 Creators:
Maganas, Dimitrios1, Author           
Kowalska, Joanna K.2, Author           
Nooijen, Marcel3, Author
DeBeer, Serena2, Author           
Neese, Frank4, Author           
Affiliations:
1Research Group Manganas, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541709              
2Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              
3Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada, ou_persistent22              
4Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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 Abstract: In this work, we present a detailed comparison of wavefunction-based multireference (MR) techniques for the prediction of transition metal L-edge X-ray absorption spectroscopy (XAS) using [Fe(II)Cl4]2− and [Fe(III)Cl4]1− complexes as prototypical test cases. We focus on the comparison of MR Configuration Interaction (MRCI) and MR Equation of Motion Coupled Cluster (MREOM-CC) methods, which are employed to calculate valence excitation as well as core to valence Fe L-edge XAS spectra of [Fe(II)Cl4]2− and [Fe(III)Cl4]1− complexes. The two investigated approaches are thoroughly analyzed with respect to their information content regarding (1) metal-ligand covalency, (2) ligand field splittings, (3) relativistic effects, (4) electron correlation, (5) energy distribution, and (6) intensity modulation of the experimentally observed spectral features. It is shown that at the level of MRCI calculations in both [Fe(II)Cl4]2− and [Fe(III)Cl4]1− cases, very good agreement with the experimental Fe L-edge XAS spectra is obtained provided that the employed active space is extended to include ligand-based orbitals in addition to metal-based molecular orbitals. It is shown that this is necessary in order to correctly describe the important σ− and π− Fe-Cl covalent interactions. By contrast, MREOM-CC calculations yield excellent agreement relative to experiment even with small active spaces. The efficiency of the employed MR computational protocols is thoroughly discussed. Overall, we believe that this study serves as an important reference for future developments and applications of MR methods in the field of X-Ray spectroscopy.

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Language(s): eng - English
 Dates: 2018-08-102019-02-062019-03-122019-03-14
 Publication Status: Published in print
 Pages: 16
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1063/1.5051613
 Degree: -

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Title: The Journal of Chemical Physics
  Other : J. Chem. Phys.
Source Genre: Journal
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Publ. Info: Woodbury, N.Y. : American Institute of Physics
Pages: - Volume / Issue: 150 (10) Sequence Number: 104106 Start / End Page: - Identifier: ISSN: 0021-9606
CoNE: https://pure.mpg.de/cone/journals/resource/954922836226