Theoretical Chemistry Division, Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria.
Inorg Chem. 2012 Jun 18;51(12):6746-52. doi: 10.1021/ic300385s. Epub 2012 May 31.
A quantum-mechanical charge-field molecular dynamics simulation has been performed for a tetravalent Ce ion in aqueous solution. In this framework, the complete first and second hydration spheres are treated by ab initio quantum mechanics supplemented by an electrostatic embedding technique, making the construction of non-Coulombic solute-solvent potentials unnecessary. During the 10 ps of simulation time, the structural aspects of the solution were analyzed by various methods. Experimental results such as the mean Ce-O bond distance and the predicted first-shell coordination number were compared to the results obtained from the simulation resolving some ambiguities in the literature. The dynamics of the system were characterized by mean ligand residence times and frequency/force constant calculations. Furthermore, Ce-O and Ce-H angular radial distribution plots were employed, yielding deeper insight into the structural and dynamical aspects of the system.
我们对四价铈离子在水溶液中的情况进行了量子力学荷场分子动力学模拟。在这个框架中，通过从头算量子力学和静电嵌入技术对完整的第一和第二水合层进行了处理，从而无需构建非库仑溶剂-溶质相互作用势。在 10 ps 的模拟时间内，我们使用各种方法分析了溶液的结构方面。将实验结果（如平均 Ce-O 键距离和预测的第一壳层配位数）与模拟结果进行了比较，解决了文献中的一些歧义。通过平均配体停留时间和频率/力常数计算来描述系统的动力学。此外，还使用了 Ce-O 和 Ce-H 角径向分布图，深入了解了系统的结构和动力学方面。
