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Title: Excited States and Luminescent Properties of UO 2F 2 and Its Solvated Complexes in Aqueous Solution

Abstract

The electronic absorption and emission spectra of free UO 2F 2 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 UO 2F 2 is explored by investigating the excited states of solvated complexes (H 2O) nUO 2F 2 (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 (H 2O) nUO 2F 2 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 UO 2F 2 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.

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1170484
Report Number(s):
PNNL-SA-101894
Journal ID: ISSN 0020-1669; 47951; KP1702030
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 53; Journal Issue: 14
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Su, Jing, Wang, Zheming, Pan, Duoqiang, and Li, Jun. Excited States and Luminescent Properties of UO2F2 and Its Solvated Complexes in Aqueous Solution. United States: N. p., 2014. Web. doi:10.1021/ic5006852.
Su, Jing, Wang, Zheming, Pan, Duoqiang, & Li, Jun. Excited States and Luminescent Properties of UO2F2 and Its Solvated Complexes in Aqueous Solution. United States. doi:10.1021/ic5006852.
Su, Jing, Wang, Zheming, Pan, Duoqiang, and Li, Jun. Mon . "Excited States and Luminescent Properties of UO2F2 and Its Solvated Complexes in Aqueous Solution". United States. doi:10.1021/ic5006852.
@article{osti_1170484,
title = {Excited States and Luminescent Properties of UO2F2 and Its Solvated Complexes in Aqueous Solution},
author = {Su, Jing and Wang, Zheming and Pan, Duoqiang and Li, Jun},
abstractNote = {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 = 1g) 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.},
doi = {10.1021/ic5006852},
journal = {Inorganic Chemistry},
number = 14,
volume = 53,
place = {United States},
year = {Mon Jul 21 00:00:00 EDT 2014},
month = {Mon Jul 21 00:00:00 EDT 2014}
}