Issue 42, 2010

Investigating the electronic structure and bonding in uranyl compounds by combining NEXAFSspectroscopy and quantum chemistry

Abstract

The nature of the reactivity of the “yl” oxygens has been a subject of constant interest for a long time in uranyl chemistry. Thus, the electron-donor ability of the equatorial ligands plays an important role in the nature of the uranyl U[double bond, length as m-dash]O bond. In this paper, a combination of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and both ground-state and time-dependent density functional theory (DFT) calculations have been used to examine the effect of equatorial plane ligation on the U[double bond, length as m-dash]O bonding in two uranyl complexes: [UO2(py)3I2] and [UO2(CN)5][NEt4]3. By coupling experimental data and theory, spectral features observed in the oxygen K-edge NEXAFS spectra have been assigned. Despite the inert character of the U[double bond, length as m-dash]O bond, we observe that the electron-donating or withdrawing character of the equatorial ligands has a measurable effect on features in the NEXAFS spectra of these species and thereby on the unoccupied molecular orbitals of {UO2}2+.

Graphical abstract: Investigating the electronic structure and bonding in uranyl compounds by combining NEXAFS spectroscopy and quantum chemistry

Article information

Article type
Paper
Submitted
28 Apr 2010
Accepted
22 Jun 2010
First published
30 Sep 2010

Phys. Chem. Chem. Phys., 2010,12, 14253-14262

Investigating the electronic structure and bonding in uranyl compounds by combining NEXAFS spectroscopy and quantum chemistry

C. Fillaux, D. Guillaumont, J. Berthet, R. Copping, D. K. Shuh, T. Tyliszczak and C. D. Auwer, Phys. Chem. Chem. Phys., 2010, 12, 14253 DOI: 10.1039/C0CP00386G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements