Structure and Spectra of UO2F2 and Its Hydrated Species

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 105; no. 36; pp. 8370 - 8375
• Main Authors: Wang, Qi, Pitzer, Russell M
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 13.09.2001
• Subjects: CONFIGURATION INTERACTION; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; ENVIRONMENTAL MOLECULAR SCIENCES LABORATORY; RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; URANYL FLUORIDES
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp004009z

The electronic spectra of UO2F2, both isolated and hydrated, have been studied using ab initio spin−orbit configuration interaction calculations based on relativistic effective core potentials. The structures of UO2F2 species were obtained by the density functional theory method. The initial structure has a (nonplanar) C 2 v geometry, while adding solvating water molecules and optimizing the structure UO2F2(H2O) n give a very stable structure for n = 4, with D 2 geometry. The ground state and some excited states were studied for UO2F2(H2O) n using the structures obtained. Electric-dipole transition moments were calculated for UO2F2(H2O)4. Spin−orbit and equatorial−ligand (F-, H2O) interactions compete in determining the splittings of the known 3Δg state of the uranyl ion, particularly the 3Δ1g luminescent state.