Quantum chemical topology and natural bond orbital analysis of M–O covalency in M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np)

Covalency is complex yet central to our understanding of chemical bonding, particularly in the actinide series. Here we assess covalency in a series of isostructural d and f transition element compounds M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np) using scalar relativistic hybrid density funct...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2020-08, Vol.22 (29), p.16804-16812
Main Authors: Berryman, Victoria E. J., Shephard, Jacob J., Ochiai, Tatsumi, Price, Amy N., Arnold, Polly L., Parsons, Simon, Kaltsoyannis, Nikolas
Format: Article
Language:English
Subjects:
Actinides
Chemical bonds
Covalence
Density functional theory
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Neptunium
Quantum chemistry
Quantum theory
Relativistic theory
Thorium
Titanium
Toolkits
Topology
Uranium
Zirconium
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Summary:Covalency is complex yet central to our understanding of chemical bonding, particularly in the actinide series. Here we assess covalency in a series of isostructural d and f transition element compounds M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np) using scalar relativistic hybrid density functional theory in conjunction with the Natural Bond Orbital (NBO), quantum theory of atoms in molecules (QTAIM) and interacting quantum atoms (IQA) approaches. The IQA exchange–correlation covalency metric is evaluated for the first time for actinides other than uranium, in order to assess its applicability in the 5f series. It is found to have excellent correlation with NBO and QTAIM covalency metrics, making it a promising addition to the computational toolkit for analysing metal–ligand bonding. Our range of metrics agree that the actinide-oxygen bonds are the most covalent of the elements studied, with those of the heavier group 4 elements the least. Within the early actinide series, Th stands apart from the other three elements considered, being consistently the least covalent.
ISSN:1463-9076
1463-9084
DOI:10.1039/d0cp02947e