title: Gas phase computational studies on the competition between nitrile and water ligands in uranyl complexes.
abstract: The gas phase formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO(2)(H(2)O)(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 [UO(2)OH(H(2)O)(m)(RCN)(n)](+) by the loss of either H(3)O(+) 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.
authors.affiliation: Department of Chemistry, Iowa State University and Ames Laboratory, Ames Iowa 50011, USA.
authors.forename: George
authors.initials: G
authors.lastname: Schoendorff
authors.forename: Wibe A
authors.initials: WA
authors.lastname: de Jong
authors.forename: Mark S
authors.initials: MS
authors.lastname: Gordon
authors.forename: Theresa L
authors.initials: TL
authors.lastname: Windus
mesh_terms: D005740:Gases / Q000737:chemistry*; D008024:Ligands; D056004:Molecular Dynamics Simulation; D009570:Nitriles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D014501:Uranium / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D005740:Gases; D008024:Ligands; D009570:Nitriles; D009942:Organometallic Compounds; D014867:Water; D014501:Uranium