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  4. Quantum Chemical Study of the Water Exchange Mechanism of the Americyl(VI) Aqua Ion
 
research article

Quantum Chemical Study of the Water Exchange Mechanism of the Americyl(VI) Aqua Ion

Fabrizio, Alberto
•
Rotzinger, Francois P.  
2016
Inorganic Chemistry

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 (Delta G(double dagger)) for the dissociative (D) and the associative interchange (I-a) 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. Delta G(double dagger) 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 I-a mechanism is preferred) due to ligand-field effects. On the basis of the present computations, it is not possible to distinguish the I-a from the D mechanism for americyl(VI). In contrast to two other theoretical studies, the dissociative mechanism cannot be ruled out.

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Type
research article
DOI
10.1021/acs.inorgchem.6b01793
Web of Science ID

WOS:000387428200038

Author(s)
Fabrizio, Alberto
•
Rotzinger, Francois P.  
Date Issued

2016

Publisher

American Chemical Society

Published in
Inorganic Chemistry
Volume

55

Issue

21

Start page

11147

End page

11152

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LPI  
Available on Infoscience
January 24, 2017
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/133654
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