Freire Ricardo O, da Costa Nivan B, Rocha Gerd B, Simas Alfredo M
Departamento de Química Fundamental, CCEN, UFPE, Recife, PE, Brazil.
J Phys Chem A. 2006 May 4;110(17):5897-900. doi: 10.1021/jp057286k.
The sparkle/AM1 model for the quantum chemical prediction of coordination polyhedron crystallographic geometries from isolated lanthanide complex ion calculations, defined recently for Eu(III), Gd(III), and Tb(III) (Inorg. Chem. 2005, 44, 3299) is now extended to La(III) and Lu(III). Thus, for each of the metal ions we chose a training set of 15 complexes that possess various representative ligands of high crystallographic quality (R factor < 0.05 Angstroms) and oxygen and/or nitrogen as coordinating atoms. In the validation procedure we used a set of 60 more La(III) coordination compound structures, as well as 15 more Lu(III) coordination compound structures, all of high crystallographic quality. For both the 75 La(III) compounds and the 30 Lu(III) compounds, the Sparkle/AM1 unsigned mean error, for all interatomic distances between the metal ions and the ligand atoms of the first sphere of coordination, is 0.08 Angstroms, thus comparable to the accuracy normally achievable by present day ab initio/ECP calculations, while being hundreds of times faster.
最近为铕（III）、钆（III）和铽（III）定义的用于从孤立镧系元素络合离子计算中对配位多面体晶体学几何结构进行量子化学预测的Sparkle/AM1模型（《无机化学》，2005年，第44卷，第3299页）现扩展至镧（III）和镥（III）。因此，对于每种金属离子，我们选择了一组由15种配合物组成的训练集，这些配合物具有各种具有高晶体学质量（R因子<0.05埃）的代表性配体，且以氧和/或氮作为配位原子。在验证过程中，我们使用了另外一组60种镧（III）配位化合物结构以及15种镥（III）配位化合物结构，所有这些结构均具有高晶体学质量。对于这75种镧（III）化合物和30种镥（III）化合物，在金属离子与第一配位层配体原子之间的所有原子间距离方面，Sparkle/AM1的无符号平均误差为0.08埃，因此与当今从头算/有效核势计算通常可达到的精度相当，同时速度要快数百倍。
