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Issue 42, 2010
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Investigating the electronic structure and bonding in uranyl compounds by combining NEXAFS spectroscopy and quantum chemistry

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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

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Publication details

The article was received on 28 Apr 2010, accepted on 22 Jun 2010 and first published on 30 Sep 2010


Article type: Paper
DOI: 10.1039/C0CP00386G
Citation: Phys. Chem. Chem. Phys., 2010,12, 14253-14262
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    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

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