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  • UO2_PDP_AK_resubmission_V2

    Rights statement: 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

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

Research output: Contribution to journalJournal article

Published
<mark>Journal publication date</mark>19/01/2016
<mark>Journal</mark>Inorganic Chemistry
Issue number2
Volume55
Number of pages11
Pages (from-to)573-583
Publication statusPublished
Early online date23/12/15
Original languageEnglish

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.

Bibliographic note

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