Abstract
The water exchange reaction of the americyl(VI) aqua ion was investigated with quantum chemical methods, density functional theory (DFT), and wave function theory (WFT). Associative and dissociative substitution mechanisms were studied, whereby DFT produced inaccurate results for the associative mechanism in contrast to WFT. The Gibbs activation energies (ΔG‡) for the dissociative (D) and the associative interchange (Ia) mechanisms, computed with WFT taking into account static and dynamic electron correlation, near-degeneracy, and spin-orbit coupling, are equal within the error limits of the calculations. ΔG‡ for the water exchange of americyl(VI) via the dissociative mechanism is considerably lower than those for uranyl(VI) and plutonyl(VI) (for which the Ia mechanism is preferred) due to ligand-field effects. On the basis of the present computations, it is not possible to distinguish the Ia from the D mechanism for americyl(VI). In contrast to two other theoretical studies, the dissociative mechanism cannot be ruled out.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
