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Theoretical study of electron transfer in uranyl(VI)–uranyl(V) complexes in solution
Author(s) -
Lu ShenZhuang
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22309
Subject(s) - uranyl , chemistry , hydroxide , fluoride , electron transfer , inorganic chemistry , ion , organic chemistry
The rates of the electron self‐exchange between uranyl(VI) and uranyl(V) complexes in solution have been investigated in detail with quantum chemical methods. The calculations have shown that the bond length of UOyl is elongated by 0.1 Å when the extra electron is localized on the sites. The diabatic potential surfaces are obtained. The inner reorganization energies are 212.6 and 226.8 kJ mol −1 for hydroxide and fluoride bridge systems, respectively. The solvent reorganization energies are 28.12 and 31.60 kJ mol −1 for hydroxide and fluoride bridge systems, respectively. The nuclear frequency factors are 3.17 × 10 13 and 3.12 × 10 13 s −1 for hydroxide and fluoride bridge systems, respectively. The electronic coupling matrix elements are 1.89 and 4.06 kJ mol −1 for hydroxide and fluoride bridge systems, respectively. The electron‐transfer rates of our calculations are 12.95 and 0.819 M −1 s −1 for hydroxide and fluoride bridge systems, respectively. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010