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  Periodic Trends in Lanthanide Compounds through the Eyes of Multireference ab Initio Theory

Aravena, D., Atanasov, M., & Neese, F. (2016). Periodic Trends in Lanthanide Compounds through the Eyes of Multireference ab Initio Theory. Inorganic Chemistry, 55(9), 4457-4469. doi:10.1021/acs.inorgchem.6b00244.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0007-84DD-B Version Permalink: http://hdl.handle.net/21.11116/0000-0007-84DE-A
Genre: Journal Article

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 Creators:
Aravena, Daniel1, Author
Atanasov, Mihail2, 3, Author              
Neese, Frank2, Author              
Affiliations:
1Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40, Correo 33, Santiago, Chile, ou_persistent22              
2Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
3Bulgarian Academy of Sciences, Institute of General and Inorganic Chemistry, Akad. Georgi Bontchev Street 11, 1113 Sofia, Bulgaria, ou_persistent22              

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 Abstract: Regularities among electronic configurations for common oxidation states in lanthanide complexes and the low involvement of f orbitals in bonding result in the appearance of several periodic trends along the lanthanide series. These trends can be observed on relatively different properties, such as bonding distances or ionization potentials. Well-known concepts like the lanthanide contraction, the double–double (tetrad) effect, and the similar chemistry along the lanthanide series stem from these regularities. Periodic trends on structural and spectroscopic properties are examined through complete active space self-consistent field (CASSCF) followed by second-order N-electron valence perturbation theory (NEVPT2) including both scalar relativistic and spin–orbit coupling effects. Energies and wave functions from electronic structure calculations are further analyzed in terms of ab initio ligand field theory (AILFT), which allows one to rigorously extract angular overlap model ligand field, Racah, and spin–orbit coupling parameters directly from high-level ab initio calculations. We investigated the elpasolite Cs2NaLnIIICl6 (LnIII = Ce–Nd, Sm–Eu, Tb–Yb) crystals because these compounds have been synthesized for most LnIII ions. Cs2NaLnIIICl elpasolites have been also thoroughly characterized with respect to their spectroscopic properties, providing an exceptionally vast and systematic experimental database allowing one to analyze the periodic trends across the lanthanide series. Particular attention was devoted to the apparent discrepancy in metal–ligand covalency trends between theory and spectroscopy described in the literature. Consistent with earlier studies, natural population analysis indicates an increase in covalency along the series, while a decrease in both the nephelauxetic (Racah) and relativistic nephelauxetic (spin–orbit coupling) reduction with increasing atomic number is calculated. These apparently conflicting results are discussed on the basis of AILFT parameters. The AILFT derived parameters faithfully reproduce the underlying multireference electronic structure calculations. The remaining discrepancies with respect to experimentally derived data are mostly due to underestimation of the ligand field splittings, while the dynamic correlation and nephelauxetic effects appears to be adequately covered by CASSCF/NEVPT2.

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Language(s): eng - English
 Dates: 2016-02-032016-04-072016-05-02
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.6b00244
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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: 55 (9) Sequence Number: - Start / End Page: 4457 - 4469 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669