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  Ab Initio Ligand-Field Theory Analysis and Covalency Trends in Actinide and Lanthanide Free Ions and Octahedral Complexes

Jung, J., Atanasov, M., & Neese, F. (2017). Ab Initio Ligand-Field Theory Analysis and Covalency Trends in Actinide and Lanthanide Free Ions and Octahedral Complexes. Inorganic Chemistry, 56(15), 8802-8816. doi:10.1021/acs.inorgchem.7b00642.

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 Creators:
Jung, Julie1, Author           
Atanasov, Mihail1, 2, Author           
Neese, Frank1, Author           
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Akad. Georgi Bontchev Street 11, 1113 Sofia, Bulgaria, ou_persistent22              

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 Abstract: Actinide chemistry is gaining increased focus in modern research, particularly in the fields of energy research and molecular magnetism. However, the structure–function and structure–property relationships of actinides have still not been studied as intensely as those for transition metals. In this work, we report a detailed ab initio study of the spectroscopic, magnetic, and bonding properties of the trivalent actinide free ions and their associated hexachloride complexes in octahedral symmetry. The electronic structures of these systems are examined using complete active-space self-consistent-field calculations followed by second-order N-electron valence perturbation theory, including both scalar relativistic and spin–orbit-coupling effects. The computed energies and wave functions are further analyzed by means of ab initio ligand-field theory (AILFT) and finally chemically interpreted by means of the angular overlap model (AOM). The derived Slater–Condon and spin–orbit parameters have allowed us to systematically rationalize the spectroscopic and magnetic properties of the investigated free ions and complexes along the entire actinide series. Overall, the AILFT- and AOM-derived parameters accurately reproduce the multireference electronic structure calculations. The small observed discrepancies with respect to experimentally derived ligand-field parameters are essentially due to an underestimation of the electronic correlation, which arises from both the constrained size of the active space (restricted to the f orbitals) and the limit of the perturbation approach to account for dynamical correlation. Our analysis also provides insight into the metal–ligand covalency trends along the series. Consistent with natural population analysis, the nephelauxetic (Slater–Condon parameters) and relativistic nephelauxetic (spin–orbit-coupling) reductions determined for these complexes indicate a decrease in the covalency along the series. These trends also hold, to varying extents, for the corresponding tetravalent derivatives, as well as the lanthanide analogues.

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Language(s): eng - English
 Dates: 2017-07-142017-08-07
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.7b00642
 Degree: -

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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 56 (15) Sequence Number: - Start / End Page: 8802 - 8816 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669