Knowledge-based design
of extracting agents for selective binding
of actinides is essential in stock-pile stewardship, environmental
remediation, separations, and nuclear fuel disposal. Robust computational
protocols are critical for in depth understanding of structural properties
and to further advance the design of selective ligands. In particular,
rapid radiochemical separations require predictive capabilities for
binding in the gas phase. This study focuses on gas-phase binding
preferences of cyclic imide dioximes to uranyl, neptunyl, plutonyl,
and americyl. Structural properties, electron withdrawing effects,
and their effects on binding preferences are studied with natural
bond-order population analysis. The aromatic amidoximes are found
to have a larger electron-donation effect than the aliphatic amidoximes.
It is also found that plutonyl is more electron withdrawing than uranyl,
neptunyl, and americyl when bound to the cyclic imide dioximes studied.