Excited States and Luminescent Properties of UO₂F₂ and Its Solvated Complexes in Aqueous Solution

Journal Article · Mon Jul 21 00:00:00 EDT 2014 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic5006852· OSTI ID:1170484

Su, Jing; Wang, Zheming; Pan, Duoqiang; Li, Jun

The electronic absorption and emission spectra of free UO₂F₂ and its water solvated complexes below 32 000 cm^–1 are investigated at the levels of ab initio CASPT2 and CCSD(T) with inclusion of scalar relativistic and spin–orbit coupling effects. The influence of the water coordination on the electronic spectra of UO₂F₂ is explored by investigating the excited states of solvated complexes (H₂O)_nUO₂F₂ (n = 1–3). In these uranyl complexes, water coordination is found to have appreciable influence on the ³Δ (Ω = 1_g) character of the luminescent state and on the electronic spectral shape. The simulated luminescence spectral curves based on the calculated spectral parameters of (H₂O)_nUO₂F₂ from CCSD(T) approach agree well with experimental spectra in aqueous solution at both near-liquid-helium temperature and room temperature. The possible luminescence spectra of free UO₂F₂ in gas phase are predicted on the basis of CASPT2 and CCSD(T) results, respectively, by considering three symmetric vibration modes. Finally, the effect of competition between spin–orbit coupling and ligand field repulsion on the luminescent state properties is discussed.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1170484
• Report Number(s): PNNL-SA-101894; 47951; KP1702030
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 14 Vol. 53; ISSN 0020-1669
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

Environmental Molecular Sciences Laboratory