Electronic Structure and Bonding in Actinyl Ions and their Analogs

Abstract

This Feature Article seeks to present the current state of knowledge, both experimental and theoretical, of the electronic structure and bonding in actinyl ions and related species, such as the isoelectronic imido compounds as well as in linear triatomic actinide molecules of the type X-An-Y.

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium

“…Denning [22] has given ad escription of the orbitalo rdering in the actinylsb uilt on experimental data for the earlier actinyls. The two lowest lying orbitals for the fe lectrons are the 1d u and the 1f u ,w hich are very close in energy and have no contribution from the oxygen 2p orbitals.…”

Charge Transfer in Uranyl(VI) Halides [UO2X4]2− (X = F, Cl, Br, and I). A Quantum Chemical Study of the Absorption Spectra

“…22 orbitals, which is still not feasible from the computational point of view. However, the spectrum of the bare uranyl ion shows that excitations below 50000 cm −1 correspond to transitions from the bonding orbitals (σ g , σ u , π g and π u ) to the empty nonbonding φ u and δ u , 10,23 which means that it is reasonable to ignore the antibonding σ * g , σ * u , π * g and π * u , as well as the nonbonding δ g (d δ ) orbitals.…”

On the multi-reference nature of plutonium oxides: PuO22+, PuO2, PuO3 and PuO2(OH)2

“…With the 5f and 6d orbitals being in the primary valence shell, actinides are able to form unique bonds and interact with other compounds in ways that no other elements are able to. [55][56][57][58][59][60] In plutonium dioxides, the 5f and 6d orbitals of the plutonium center interact with the valence orbitals on the oxygen atoms, with the exception of four pairwise degenerate nonbonding orbitals: the doubly degenerate δ u , φ u and δ g orbitals. [55].…”