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

详细信息    查看全文

• 作者：Jing Su ; Zheming Wang ; Duoqiang Pan ; Jun Li
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：July 21, 2014
• 年：2014
• 卷：53
• 期：14
• 页码：7340-7350
• 全文大小：421K
• ISSN：1520-510X

文摘

The electronic absorption and emission spectra of free UO₂F₂ and its water solvated complexes below 32鈥?00 cm^鈥? are investigated at the levels of ab initio CASPT2 and CCSD(T) with inclusion of scalar relativistic and spin鈥搊rbit 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鈥?). In these uranyl complexes, water coordination is found to have appreciable influence on the ³螖 (惟 = 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. The effect of competition between spin鈥搊rbit coupling and ligand field repulsion on the luminescent state properties is discussed.