Emission spectroscopy of uranium(IV) compounds:a combined synthetic, spectroscopic and computational study

Hashem, Emtithal and Swinburne, Adam N. and Schulzke, Carola and Evans, Rachel C. and Platts, James A. and Kerridge, Andrew and Natrajan, Louise S. and Baker, Robert J. (2013) Emission spectroscopy of uranium(IV) compounds:a combined synthetic, spectroscopic and computational study. RSC Advances, 3 (13). pp. 4350-4361. ISSN 2046-2069

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Emission spectroscopy has been used for the first time in a spectroscopic study of a family of uranium(IV) halide complexes in non-aqueous media. The room temperature electronic absorption spectra of the simple coordination compounds [Li(THF)(4)][UX5(THF)] (X = Cl, Br, I), [Et4N](2)[UCl6] and UCl4 in THF have been recorded and all transitions assigned with the aid of a comprehensive computational study using CASSCF and CASPT2 techniques. Excitation into a band of f-d and LMCT character followed by energy transfer into the 5f-orbital manifold accounts for the UV-visible radiative transitions observed in the emission spectra, which have been fully assigned as arising from transitions from the 5f(1)6d(1) electronic configuration to envelopes of states arising from the ground state 5f(2) configuration. The bonding in [Li(THF)(4)][UCl5(THF)] has been further elucidated utilising NBO and AIM calculations which describe the nature of the U-Cl bond as predominantly ionic with some dative covalent character and substantial overlap between the Cl 3p orbitals and 5f and 6d orbitals on uranium. These studies indicate that the emission spectral fingerprint of simple U(IV) compounds of O-h, C-4v and C-2v symmetry are similar and characteristic and may be used as a diagnostic tool to assign U(IV) species in solution and by inference, in the environment, in the presence of [UO2](2+).

Item Type: Journal Article
Journal or Publication Title: RSC Advances
Uncontrolled Keywords: /dk/atira/pure/subjectarea/asjc/1600
ID Code: 71569
Deposited By: ep_importer_pure
Deposited On: 03 Nov 2014 14:20
Refereed?: Yes
Published?: Published
Last Modified: 19 Feb 2020 08:19
URI: https://eprints.lancs.ac.uk/id/eprint/71569

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