title: Water exchange mechanism in the first excited state of hydrated uranyl(VI).
abstract: The water exchange mechanism of the uranyl(VI) aquo ion in the luminescent state, (3)Delta(g) 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 in the 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 0.5 x 10(6) s(-1) and 1.3 x 10(6) s(-1), respectively.
authors.affiliation: Department of Physics, Stockholm University, AlbaNova University Centre, 106 91 Stockholm, Sweden.
authors.forename: Pernilla
authors.initials: P
authors.lastname: Wåhlin
authors.forename: Valérie
authors.initials: V
authors.lastname: Vallet
authors.forename: Ulf
authors.initials: U
authors.lastname: Wahlgren
authors.forename: Ingmar
authors.initials: I
authors.lastname: Grenthe