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

Abstract

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.

Authors:
; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
969612
Report Number(s):
PNNL-SA-65969
Journal ID: ISSN 1089-5639; 29990; KC0302030; TRN: US1000281
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A, 113(45):12525-12531
Additional Journal Information:
Journal Volume: 113; Journal Issue: 45; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; URANYL COMPLEXES; DENSITY FUNCTIONAL METHOD; NITRILES; CARBONYLS; BINDING ENERGY; SPECTROSCOPY; nitrile ligands; carbonyl ligands; density functional theory; formaldehyde; uranyl; Environmental Molecular Sciences Laboratory

Citation Formats

Schoendorff, George E, Windus, Theresa L, and De Jong, Wibe A. Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives. United States: N. p., 2009. Web. doi:10.1021/jp9038623.
Schoendorff, George E, Windus, Theresa L, & De Jong, Wibe A. Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives. United States. doi:10.1021/jp9038623.
Schoendorff, George E, Windus, Theresa L, and De Jong, Wibe A. Sat . "Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives". United States. doi:10.1021/jp9038623.
@article{osti_969612,
title = {Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives},
author = {Schoendorff, George E and Windus, Theresa L and De Jong, Wibe A},
abstractNote = {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.},
doi = {10.1021/jp9038623},
journal = {Journal of Physical Chemistry A, 113(45):12525-12531},
issn = {1089-5639},
number = 45,
volume = 113,
place = {United States},
year = {2009},
month = {12}
}