Frick Robert J, Pribil Andreas B, Hofer Thomas S, Randolf Bernhard R, Bhattacharjee Anirban, Rode Bernd M
Theoretical Chemistry Division, Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria.
Inorg Chem. 2009 May 4;48(9):3993-4002. doi: 10.1021/ic801554p.
The structure and dynamics of the stable four-times positively charged uranium(IV) cation in aqueous solution have been investigated by ab initio quantum mechanical charge field (QMCF) molecular dynamics (MD) simulation at the Hartree-Fock double-zeta quantum mechanical level. The QMCF-MD approach enables investigations with the accuracy of a quantum mechanics/molecular mechanics approach without the need for the construction of solute-solvent potentials. Angular distribution functions; radial distribution functions; coordination numbers of the first, second, and third shell (9, 19, and 44, respectively); coordination number distribution functions; tilt- and Theta-angle distribution functions; as well as local density corrected triangle distribution functions have been employed for the evaluation of the hydrated ion's structure. Special attention was paid to the determination of the geometry of the first hydration layer, and the results were compared to experimental large-angle X-ray scattering and extended X-ray absorption fine structure data. The solvent dynamics around the ion were also investigated using mean ligand residence times and related data and, resulting from the unavailability of any experimental data, were compared to ions with similar properties.
在哈特里 - 福克双ζ量子力学水平上，通过从头算量子力学电荷场（QMCF）分子动力学（MD）模拟，研究了水溶液中稳定的四倍带正电荷的铀（IV）阳离子的结构和动力学。QMCF - MD方法能够以量子力学/分子力学方法的精度进行研究，而无需构建溶质 - 溶剂势。角分布函数、径向分布函数、第一、第二和第三壳层的配位数（分别为9、19和44）、配位数分布函数、倾斜角和θ角分布函数，以及局部密度校正三角形分布函数已被用于评估水合离子的结构。特别关注了第一水合层几何结构的确定，并将结果与实验大角度X射线散射和扩展X射线吸收精细结构数据进行了比较。还使用平均配体停留时间和相关数据研究了离子周围的溶剂动力学，由于没有任何实验数据，将其与具有相似性质的离子进行了比较。
