The Water Exchange Mechanism in the First Excited State of Hydrated Uranyl(VI)

Wåhlin, Pernilla; Vallet, Valérie; Wahlgren, Ulf; Grenthe, Ingmar

Document type :

Article dans une revue scientifique

DOI :

10.1021/ic9017689

Title :

The Water Exchange Mechanism in the First Excited State of Hydrated Uranyl(VI)

Author(s) :

Wåhlin, Pernilla [Auteur]
Vallet, Valérie [Auteur]

Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 [PhLAM]
Wahlgren, Ulf [Auteur]
Nordic Institute for Theoretical Physics [NORDITA]
Grenthe, Ingmar [Auteur]

Journal title :

INORGANIC CHEMISTRY

Pages :

11310

Publisher :

American Chemical Society

Publication date :

2009-10-30

ISSN :

0020-1669

English keyword(s) :

actinide
ab initio
uranyl
water exchange

HAL domain(s) :

Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]

English abstract : [en]

The water exchange mechanism of the uranyl(VI) aquo ion in the luminescent state, 3Δg in the spin-orbit free nomenclature, has been investigated using quantum chemical methods and compared to the ...
Show more >The water exchange mechanism of the uranyl(VI) aquo ion in the luminescent state, 3Δg in the spin-orbit free nomenclature, has been investigated using quantum chemical methods and compared to the corresponding reaction in the electronic ground state. The reaction mechanism was studied by calculation of the enthalpy of reaction of the A and D intermediates relative to the reactant, using a penta-aquo ion model with one additional water molecule in the second hydration sphere. The reaction barriers around the intermediates are low and they are therefore a good approximation for the activation enthalpy. The energy of the D-intermediate is significantly larger than that of the A-intermediate both in the luminescent and ground states, suggesting that the water exchange is the same in both states. This suggestion is supported by the experimental rate constants for luminescence decay and water exchange in the electronic ground state that are 0.5x106 s-1 and 1.3x106 s-1, respectively.Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

Comment :

4 pages

Collections :

Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM) - UMR 8523

Source :

Harvested from HAL

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