Abstract
In the present study the structural, vibrational and bonding properties of the uranium(VI) halide and oxyhalide molecules UX 6 and UO 2X 2 (X=F, Cl, Br, I) have been investigated by quantum chemical calculations. The title molecular properties have been computed using quasi-relativistic density functional theory in conjunction with a polarised triple-zeta basis set. The bonding interactions between the fragments U⋯X 6 and UO 2⋯X 2 have been investigated using the extended transition state energy partitioning method. Our quantitative analysis revealed an increase of the electrostatic interactions in UO 2X 2 with respect to UX 6 as a result of the oxygen substitution. Analogously to previous results on uranyl, the bonding Kohn–Sham orbitals of UO 2X 2 showed a clear triple-bond character of the formally UO double bonds. The population analysis results are in agreement with a predominant role of the uranium 5f orbitals in the orbital interactions, whereas a slight strengthening of the 6d contributions toward the heavier halides.
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