论文部分内容阅读
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n和m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.
The structure of non-hydrated and hydrated uranyl carbonate compounds Cn / m (where n and m are the number of carbonic acid ligands and water ligands, respectively) in aqueous solution was systematically investigated by using relativistic density functional theory. The solvent effect (COSMO) is considered, and the zero order regular approximation (ZORA) method is used to consider the relativistic effects of scalar relativities and the spin-orbit coupling relativistic effects.The electronic transitions are modeled by the time-dependent density functional theory The exchange potential is calculated using the statistical approximation of the orbital potential energy (SAOP). The results show that the carbonic acid ligand has a great influence on the structure and electron transition of the complex. The stability of the C3 / 0 complex can be attributed to the 5f orbit involved in the high occupied orbit The addition of carbonate ligand results in a blue shift of the maximum wavelength and a high intensity of absorption in the near-visible region.