Theoretical Chemistry Division Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck , Innrain 80-82, A-6020 Innsbruck, Austria.
J Phys Chem B. 2013 Dec 5;117(48):15151-6. doi: 10.1021/jp410284z. Epub 2013 Nov 22.
Structural and dynamical properties of the erbium(III) ion in water have been obtained by means of ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) simulations for the ground state and an excited state. The quality of the simulations has been monitored by recording UV/vis and Raman spectra of dilute solutions of ErCl3 and Er(NO3)3 in water and by comparison with EXAFS data from literature. Slight deviations between these data can be mainly attributed to relativistic effects, which are not sufficiently considered by the methodological framework. In both simulations, a mixture of coordination numbers eight and nine and a ligand exchange on the picosecond range are observed. The strength of the Er-ligand bond is considerably lower than that of trivalent transition metal ions but higher than that for La(III) and Ce(III) in aqueous solution. The main difference between ground state and excited state is the ligand exchange rate of the first shell. The second hydration shell is stable in both cases but with significantly different properties.
通过从头算电荷场分子动力学(QMCF-MD)模拟，获得了基态和激发态下水中铒(III)离子的结构和动力学性质。通过记录 ErCl3 和 Er(NO3)3 在水中的稀溶液的紫外/可见和拉曼光谱，并与文献中的 EXAFS 数据进行比较，监测了模拟的质量。这些数据之间的细微偏差主要归因于相对论效应，而方法框架没有充分考虑到这些效应。在这两种模拟中，观察到配位数为 8 和 9 的混合物和皮秒范围内的配体交换。铒配体键的强度远低于三价过渡金属离子，但高于水溶液中的 La(III)和 Ce(III)。基态和激发态之间的主要区别在于第一壳层的配体交换率。在这两种情况下，第二水合壳层都是稳定的，但具有明显不同的性质。
