ELECTRONIC-STRUCTURE AND X-RAY PHOTOELECTRON-SPECTRA OF URANYL COMPOUNDS

The relativistic discrete variation method (RDVM) is used to calculate MO energies and charge density distributions of the clusters UO2O46-, UO2Cl42-, and UO2F64- in the uranyl compounds gamma-UO3, Cs2UO2Cl4, and UO2F2, respectively. The role of relativistic effects in these systems is evaluated by comparing the relativistic and nonrelativistic DVM calculations. The energies and MO structure are used to interpret x-ray photoelectron spectra of three uranyl compounds. The agreement attained between theory and experiment is consistent with significant interaction of U 6p with O, F 2s, and Cl 3s AO and valence states.