U−Oyl stretching vibrations as a quantitative measure of the equatorial bond covalency in uranyl complexes:a quantum-chemical investigation

Di Pietro, Poppy and Kerridge, Andrew (2016) U−Oyl stretching vibrations as a quantitative measure of the equatorial bond covalency in uranyl complexes:a quantum-chemical investigation. Inorganic Chemistry, 55 (2). pp. 573-583. ISSN 0020-1669

[img]
Preview
PDF (UO2_PDP_AK_resubmission_V2)
UO2_PDP_AK_resubmission_V2.pdf - Accepted Version
Available under License Creative Commons Attribution.

Download (1MB)

Abstract

The molecular structures of a series of uranyl (UO22+) complexes in which the uranium center is equatorially coordinated by a first-row species are calculated at the density functional theory level and binding energies deduced. The resulting electronic structures are investigated using a variety of density-based analysis techniques in order to quantify the degree of covalency in the equatorial bonds. It is shown that a consideration of the properties of both the one-electron and electron-pair densities is required to understand and rationalize the variation in axial bonding effected by equatorial complexation. Strong correlations are found between density-based measures of the covalency and equatorial binding energies, implying a stabilizing effect due to covalent interaction, and it is proposed that uranyl U–Oyl stretching vibrational frequencies can serve as an experimental probe of equatorial covalency.

Item Type:
Journal Article
Journal or Publication Title:
Inorganic Chemistry
Additional Information:
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright ©2015 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b01219
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1600/1604
Subjects:
ID Code:
78272
Deposited By:
Deposited On:
19 Feb 2016 16:34
Refereed?:
Yes
Published?:
Published
Last Modified:
09 Apr 2020 02:34