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Inorganics 2018, 6(3), 88; https://doi.org/10.3390/inorganics6030088

Decomposition of d- and f-Shell Contributions to Uranium Bonding from the Quantum Theory of Atoms in Molecules: Application to Uranium and Uranyl Halides

1
Department of Chemistry, Lancaster University, Lancaster LA1 4YB, UK
2
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK
*
Author to whom correspondence should be addressed.
Received: 7 August 2018 / Revised: 14 August 2018 / Accepted: 20 August 2018 / Published: 30 August 2018
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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Abstract

The electronic structures of a series of uranium hexahalide and uranyl tetrahalide complexes were simulated at the density functional theoretical (DFT) level. The resulting electronic structures were analyzed using a novel application of the Quantum Theory of Atoms in Molecules (QTAIM) by exploiting the high symmetry of the complexes to determine 5f- and 6d-shell contributions to bonding via symmetry arguments. This analysis revealed fluoride ligation to result in strong bonds with a significant covalent character while ligation by chloride and bromide species resulted in more ionic interactions with little differentiation between the ligands. Fluoride ligands were also found to be most capable of perturbing an existing electronic structure. 5f contributions to overlap-driven covalency were found to be larger than 6d contributions for all interactions in all complexes studied while degeneracy-driven covalent contributions showed significantly greater variation. σ-contributions to degeneracy-driven covalency were found to be consistently larger than those of individual π-components while the total π-contribution was, in some cases, larger. Strong correlations were found between overlap-driven covalent bond contributions, U–O vibrational frequencies, and energetic stability, which indicates that overlap-driven covalency leads to bond stabilization in these complexes and that uranyl vibrational frequencies can be used to quantitatively probe equatorial bond covalency. For uranium hexahalides, degeneracy-driven covalency was found to anti-correlate with bond stability. View Full-Text
Keywords: uranium; uranyl; halide; covalency; QTAIM; CASSCF; DFT; electron density uranium; uranyl; halide; covalency; QTAIM; CASSCF; DFT; electron density
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Tanti, J.; Lincoln, M.; Kerridge, A. Decomposition of d- and f-Shell Contributions to Uranium Bonding from the Quantum Theory of Atoms in Molecules: Application to Uranium and Uranyl Halides. Inorganics 2018, 6, 88.

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