Citation: Hu Shuxian. Theoretical Studies on Electronic Structure and Chemical Bonding of Actinyl Crown Ether Complexes[J]. Chemistry, ;2020, 83(2): 105-110. shu

Theoretical Studies on Electronic Structure and Chemical Bonding of Actinyl Crown Ether Complexes

Hu Shuxian

Department of Physics, University of Science and Technology Beijing, Beijing, 100083

Received Date: 27 October 2019
Accepted Date: 10 November 2019

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In this mini-review, we have briefly summarized the theoretical research on geometrical structures and coordination chemistry of actinide complexes, the electronic structures of actinyl-crown-ether complexes, and the basic principle for chemical bonding of actinyl complexes. Although increasingly numerous spectroscopy and crystallography data had been available experimentally, there were lack of systematic investigations on theoretically electronic structure and chemical bonding of actinide complexes. Herein reviewed are our recently works from computational chemistry modeling on the coordination structures, stabilization energies and spectra properties of actinyl-crown-ether complexes. Our research has shown that the in-cavity complexes and their bonding features between (thio)-crown ethers and f-elements exhibit conventional conformations, with typical An≡O_actinyl and An-O_ligand and An-S_ligand distances. The typical ionic An-Oligand and An-S_ligand bonds with an extent of covalent interaction between the An and ligand donor atoms primarily attributable to the overlap degree of radial distribution of valence atomic orbitals. From U to Cm, LMCT is gradually significant, resulting in the decrease of the formal oxidation state of Am and Cm, and the weakening of the interaction between metal ions and ligands. This periodicity of chemical bonding and the metal oxidation state provide fundamental guidance for the design of reasonable and efficient ligands in the application of lanthanide-actinide separation.
- Actinide compounds,
- Crown ether,
- Electronic structure,
- Lanthanide-actinide separation,
- Computational chemistry
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