Equatorial Electronic Structure in the Uranyl Ion: CsUOCl and CsUOBr.

Electric field gradient (EFG) tensors in the equatorial plane of the linear UO ion have been measured by nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) experiments and computed by relativistic Kohn-Sham methods with and without environment embedding for CsUOCl and CsUOBr. This approach expands the possibilities for probing the electronic structure in uranyl complexes beyond the strongly covalent U-O bonds. The combined analyses find that one of the two largest principal EFG tensor components at the halogen sites points along the U-X bond (X = Cl, Br), and the second is parallel to the UO ion; in CsUOCl, the components are nearly equal in magnitude, whereas in CsUOBr, due to short-range bromide-cesium interactions, the equatorial component is dominant for one pair of Br sites and the axial component is larger for the second pair. The directions and relative magnitudes of the field gradient principal axes are found to be sensitive to the σ and π electron donation by the ligands and the model of the environment. Chlorine-35 NQR spectra of U-depleted and U-enriched CsUOCl exhibited no uranium-isotope-dependent shift, but the resonance of the depleted sample displayed a 58% broader line width.