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

Journal Article · · Journal of Physical Chemistry A, 113(45):12525-12531
DOI:https://doi.org/10.1021/jp9038623· OSTI ID:969612

The coordination of nitrile (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, ethanal, and acetone) ligands to the uranyl dication (UO22+) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing up to six ligands have been modeled for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that five coordinate complexes are predominant while a six coordinate complex involving propionitrile 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, in general, nitriles bind more strongly to uranyl than carbonyls.

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:
969612
Report Number(s):
PNNL-SA-65969; 29990; KC0302030
Journal Information:
Journal of Physical Chemistry A, 113(45):12525-12531, Journal Name: Journal of Physical Chemistry A, 113(45):12525-12531 Journal Issue: 45 Vol. 113; ISSN 1089-5639
Country of Publication:
United States
Language:
English

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