Gas Phase Computational Studies on the Competition between Nitrite and Water Ligands in Uranyl Complexes

TitleGas Phase Computational Studies on the Competition between Nitrite and Water Ligands in Uranyl Complexes
Publication TypeJournal Article
Year of Publication2010
AuthorsSchoendorff G, de Jong WA, Gordon MS, Windus TL
Journal TitleJournal of Physical Chemistry A
Volume114
Pages8902-8912
Date Published08/26
ISBN Number1089-5639
Accession NumberISI:000280962400047
Keywordsacidity, density, dynamics, energy-adjusted pseudopotentials, EXCHANGE, METAL-IONS, parameter sets, stability
Abstract

The gas phase formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO2(H2O)(m)(RCN)(n)](2+), has been studied using density functional theory with a relativistic effective core potential to account for scalar relativistic effects on uranium It is shown that nitrile addition is favored over the addition of water ligands Decomposition of these complexes to [UO2OH(H2O)(m)(RCN)(n)](+) by the loss of either H3O+ or (RCN + H)(+) is also examined. It is found that this reaction is competitive with the ligand addition when the coordination sphere of uranyl is unsaturated. Additionally, this reaction is influenced by the size of the nitrile ligand with reactions involving acetonitrile being the most prevalent Finally, ligand addition to the monocation shows trends similar to that of the dication with energetic differences being smaller for the addition to the monocation.

URL<Go to ISI>://000280962400047
DOI10.1021/Jp103227x