Assessing covalency in Cerium and Uranium hexachlorides:a correlated wavefunction and density functional theory study

Beekmeyer, Reece and Kerridge, Andrew (2015) Assessing covalency in Cerium and Uranium hexachlorides:a correlated wavefunction and density functional theory study. Inorganics, 3 (4). pp. 482-499. ISSN 2304-6740

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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.

Item Type:
Journal Article
Journal or Publication Title:
Inorganics
Additional Information:
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Subjects:
ID Code:
76638
Deposited By:
Deposited On:
17 Nov 2015 09:54
Refereed?:
Yes
Published?:
Published
Last Modified:
09 Jul 2020 04:03