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Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives

TitleDensity Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives
Publication TypeJournal Article
Year of Publication2009
AuthorsSchoendorff G, Windus TL, de Jong WA
Journal TitleJournal of Physical Chemistry A
Volume113
Pages12525-12531
Date Published11/12
ISBN Number1089-5639
Accession NumberISI:000271428100025
Keywordschemistry, collision-induced dissociation, dication, effective core potentials, energy-adjusted pseudopotentials, gas-phase, hydration, hydroxide complexes, oxidation, parameter sets
Abstract

The coordination of nitrite (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, acetaldehyde, and acetone) ligands to the Uranyl dication (UO22+) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing LIP to Six ligands have been modeled in the gas phase for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that 5-coordinate complexes are predominant, while 6-coordinate complexes involving propionitrile and acetone ligands might be possible. Additionally, the relative binding energy and the weakening of the uranyl bond is related to the size of the ligand, and ill general, nitrites bind more strongly to uranyl than carbonyls.
URL<Go to ISI>://000271428100025
DOI10.1021/Jp9038623