Gas Phase Computational Studies on the Competition Between Nitrile and Water Ligands in Uranyl Complexes

Journal Article · Thu Aug 26 04:00:00 UTC 2010 · Journal of Physical Chemistry A, 114(33):8902-8912

DOI:https://doi.org/10.1021/jp103227x· OSTI ID:988643

Schoendorff, George E; De Jong, Wibe A; Gordon, Mark S; Windus, Theresa L

The formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO2(H2O)n(RCN)m]2+, has been studied using density functional theory (DFT) with a relativistic effective core potential (RECP) 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)n(RCN)m]+ by the loss of either H3O+ or (RCN+H)+ is also examined. It is found that this reaction occurs 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.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 988643
• Report Number(s): PNNL-SA-71786; 29990; KP1704020
• Journal Information: Journal of Physical Chemistry A, 114(33):8902-8912, Journal Name: Journal of Physical Chemistry A, 114(33):8902-8912 Journal Issue: 33 Vol. 114
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACETONITRILE
Environmental Molecular Sciences Laboratory
FUNCTIONALS
NITRILES
SCALARS
URANIUM
URANYL COMPLEXES
WATER