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

Abstract

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.

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
988643
Report Number(s):
PNNL-SA-71786
29990; KP1704020; TRN: US201018%%597
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A, 114(33):8902-8912
Additional Journal Information:
Journal Volume: 114; Journal Issue: 33
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETONITRILE; FUNCTIONALS; NITRILES; SCALARS; URANIUM; URANYL COMPLEXES; WATER; Environmental Molecular Sciences Laboratory

Citation Formats

Schoendorff, George E, De Jong, Wibe A, Gordon, Mark S, and Windus, Theresa L. Gas Phase Computational Studies on the Competition Between Nitrile and Water Ligands in Uranyl Complexes. United States: N. p., 2010. Web. doi:10.1021/jp103227x.
Schoendorff, George E, De Jong, Wibe A, Gordon, Mark S, & Windus, Theresa L. Gas Phase Computational Studies on the Competition Between Nitrile and Water Ligands in Uranyl Complexes. United States. doi:10.1021/jp103227x.
Schoendorff, George E, De Jong, Wibe A, Gordon, Mark S, and Windus, Theresa L. Thu . "Gas Phase Computational Studies on the Competition Between Nitrile and Water Ligands in Uranyl Complexes". United States. doi:10.1021/jp103227x.
@article{osti_988643,
title = {Gas Phase Computational Studies on the Competition Between Nitrile and Water Ligands in Uranyl Complexes},
author = {Schoendorff, George E and De Jong, Wibe A and Gordon, Mark S and Windus, Theresa L},
abstractNote = {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.},
doi = {10.1021/jp103227x},
journal = {Journal of Physical Chemistry A, 114(33):8902-8912},
number = 33,
volume = 114,
place = {United States},
year = {2010},
month = {8}
}