Electron transfer in uranyl(VI)-uranyl(V) complexes in solution.
The rates and mechanisms of the electron self-exchange between U(V) and U(VI) in solution have been studied with quantum chemical methods. Both outer-sphere and inner-sphere mechanisms have been investigated; the former for the aqua ions, the latter for binuclear complexes containing hydroxide, fluoride, and carbonate as bridging ligand. The calculated rate constant for the self-exchange reaction UO(2)(+)(aq) + UO(2)(2+)(aq) <=>UO(2)(2+)(aq) + UO(2)(+)(aq), at 25 degrees C, is k = 26 M(-1) s(-1). The lower limit of the rate of electron transfer in the inner-sphere complexes is estimated to be in the range 2 x 10(4) to 4 x 10(6) M(-1) s(-1), indicating that the rate for the overall exchange reaction may be determined by the rate of formation and dissociation of the binuclear complex. The activation energy for the outer-sphere model calculated from the Marcus model is nearly the same as that obtained by a direct calculation of the precursor- and transition-state energy. A simple model with one water ligand is shown to recover 60% of the reorganization energy. This finding is important because it indicates the possibility to carry out theoretical studies of electron-transfer reactions involving M(3+) and M(4+) actinide species that have eight or nine water ligands in the first coordination sphere.
Department of Chemistry, Organic and Inorganic Chemistry, The Royal Institute of Technology, S-10044 Stockholm, Sweden.
Timofei
T
Privalov
Peter
P
Macak
Bernd
B
Schimmelpfennig
Emmanuel
E
Fromager
Ingmar
I
Grenthe
Ulf
U
Wahlgren