物理化学学报 >> 2012, Vol. 28 >> Issue (04): 792-798.doi: 10.3866/PKU.WHXB201201171

理论与计算化学 上一篇    下一篇

水溶液中碳酸铀酰化合物的电子结构

辜家芳1, 陆春海2, 陈文凯1, 陈勇1, 许可1, 黄昕1, 章永凡1   

  1. 1. 福州大学化学系, 福州 350108;
    2. 成都理工大学核技术与自动化工程学院, 成都 610059
  • 收稿日期:2011-09-26 修回日期:2012-01-08 发布日期:2012-03-21
  • 通讯作者: 陈文凯 E-mail:qc2008@fzu.edu.cn
  • 基金资助:

    国家自然科学基金(10676007)和福建省高等学校新世纪优秀人才计划(HX2006-103)资助项目

Electronic Structures of Uranyl(VI) Carbonate Complexes in the Aqueous Phase

GU Jia-Fang1, LU Chun-Hai2, CHEN Wen-Kai1, CHEN Yong1, XU Ke1, HUANG Xin1, ZHANG Yong-Fan1   

  1. 1. Department of Chemistry, Fuzhou University, Fuzhou 350108, P. R. China;
    2. College of Nuclear Technology and Automation Engineering, Chengdu University of Technology, Chengdu 610059, P. R. China
  • Received:2011-09-26 Revised:2012-01-08 Published:2012-03-21
  • Contact: CHEN Wen-Kai E-mail:qc2008@fzu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (10676007) and Program for New Century Excellent Talents at the University of Fujian Province, China (HX2006-103).

摘要: 应用相对论密度泛函理论系统研究了水溶液中非水合化和水合化碳酸铀酰化合物Cn/m(其中nm分别为结构中碳酸配体和水配体的个数)的结构. 溶剂效应采用类导体屏蔽模型(COSMO), 并采用零级规整近似(ZORA)方法考虑标量相对论效应和旋-轨耦合相对论效应. 电子跃迁采用包含旋-轨耦合相对论效应的含时密度泛函理论并在相关交换势中采用轨道势能统计平均(SAOP)做近似计算. 结果表明碳酸配体对配合物结构和电子跃迁有很大的影响. C3/0 配合物的稳定性可归于5f 轨道参与了高占据轨道的成键作用. 增加碳酸盐配体导致最大波长的蓝移, 并在近可见光区域出现高强度的吸收.

关键词: 铀酰, UV-Vis, 溶剂效应, 含时密度泛函理论, 旋-轨耦合相对论效应

Abstract: A systematic study of series of non-hydrated and hydrated Cn/m uranyl carbonate complexes (n is number of carbonate ligands, and m is number of water molecules) in the aqueous phase was carried out using relativistic density functional theory. The conductor-like screening model was used to calculate solvent effects. The zeroth-order regular approximation was used to account for scalar relativistic effects and spin-orbit coupling relativistic effects. Time-dependent density functional theory with the inclusion of spin-orbit coupling relativistic effects was used to calculate electronic transitions using the statistically averaged orbital potentials. The results indicate that carbonate ligands play an important role in the geometric and electronic transition properties of the complex. The stability of the C3/0 carbonate complex in the aqueous phase may be attributed to the involvement of 5f components in the highest occupied bonding orbital. The addition of carbonate ligands caused a blue shift in the maximum wavelength and high intensity absorptions in the near visible region.

Key words: Uranyl, UV-Vis, Solvent effect, Time-dependent density functional theory, Spin-orbit coupling relativistic effect

MSC2000: 

  • O641