Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

7-2010

Journal or Book Title

Journal of Physical Chemistry A

Volume

114

Issue

33

First Page

8902

Last Page

8912

DOI

10.1021/jp103227x

Abstract

The gas phase formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO2(H2O)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 [UO2OH(H2O)m(RCN)n]+ by the loss of either H3O+ 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.

Comments

Reprinted (adapted) with permission from J. Phys. Chem. A, 2010, 114 (33), pp 8902–8912. Copyright 2010 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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