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Inorganics 2015, 3(4), 482-499; doi:10.3390/inorganics3040482

Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study

1
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
2
Department of Chemistry, Lancaster University, Lancaster LA1 4YW, UK
*
Author to whom correspondence should be addressed.
Academic Editors: Stephen Mansell and Steve Liddle
Received: 14 September 2015 / Revised: 29 October 2015 / Accepted: 30 October 2015 / Published: 9 November 2015
(This article belongs to the Special Issue Rare Earth and Actinide Complexes)
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Abstract

The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT) levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character was studied using topological and integrated analysis based on the quantum theory of atoms in molecules (QTAIM). This analysis revealed that M–Cl covalency was strongly dependent on oxidation state, with greater covalency found in higher oxidation state complexes. Comparison of M–Cl delocalisation indices revealed a discrepancy between correlated wavefunction and DFT-derived values. Decomposition of these delocalisation indices demonstrated that the origin of this discrepancy lay in ungerade contributions associated with the f-manifold which we suggest is due to self-interaction error inherent to DFT-based methods. By all measures used in this study, extremely similar levels of covalency between complexes of U and Ce in the same oxidation state was found. View Full-Text
Keywords: covalency; cerium; uranium; CASSCF; electron density; QTAIM; DFT covalency; cerium; uranium; CASSCF; electron density; QTAIM; DFT
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Beekmeyer, R.; Kerridge, A. Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study. Inorganics 2015, 3, 482-499.

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