DV-X{alpha} investigations of the electronic structures of f{sup 1} actinide complexes
- Ohio State Univ., Columbus, OH (United States)
Complexes of the early actinide elements that contain the metal in a formal oxidation state one less than the group valence possess a single metal-localised electron outside a radon core. The authors have investigated a number of such systems, employing a fully-relativistic implementation of the DV-X{alpha} molecular orbital calculational method, as well as a non-relativistic approach for comparative purposes. The transition state formalism has been used to calculate electronic transition energies for the octahedral complexes PaF{sub 6}{sup {minus}2} and UF{sub 6}{sup {minus}2}. The results are in excellent agreement with the experimentally determined electronic absorption spectra. A similar approach has been brought to the tetrahedral Pa(BH{sub 4}){sub 4} and Pa(BH{sub 3}CH{sub 3}{sub 4}, which represent the only known examples of f{sup 1} metal centers in tetrahedral ligand fields. [{eta}{sup 8}-C{sub 8}H{sub 8}){sub 2}Pa] has also been investigated, in an attempt to establish the extent of Pa 5f and 6d atomic orbital covalency in the e{sub 2u} and e{sub 2g} metal-ring bonding levels.
- OSTI ID:
- 140990
- Report Number(s):
- CONF-930304--
- Country of Publication:
- United States
- Language:
- English
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