Sparkle/PM3 parameters for the modeling of neodymium(III), promethium(III), and samarium(III) complexes

作者：Freire Ricardo O; da Costa Nivan B Jr; Rocha Gerd B; Simas Alfredo M^*

来源：Journal of Chemical Theory and Computation, 2007, 3(4): 1588-1596.

DOI：10.1021/ct600326m

The Sparkle/PM3 model is extended to neodymium(III), promethium(III), and samarium(III) complexes. The unsigned mean error, for all Sparkle/PM3 interatomic distances between the trivalent lanthanide ion and the ligand atoms of the first sphere of coordination, is 0.074 A for Nd(III); 0.057 A for Pm(III); and 0.075 A for Sm(III). These figures are similar to the Sparkle/AM1 ones of 0.076 A, 0.059 A, and 0.075 A, respectively, indicating they are all comparable models. Moreover, their accuracy is similar to what can be obtained by present-day ab initio effective potential calculations on such lanthanide complexes. Hence, the choice of which model to utilize will depend on the assessment of the effect of either AM1 or PM3 on the quantum chemical description of the organic ligands. Finally, we present a preliminary attempt to verify the geometry prediction consistency of Sparkle/PM3. Since lanthanide complexes are usually flexible, we randomly generated 200 different input geometries for the samarium complex QIPQOV which were then fully optimized by Sparkle/PM3. A trend appeared in that, on average, the lower the total energy of the local minima found, the lower the unsigned mean errors, and the higher the accuracy of the model. These preliminary results do indicate that attempting to find, with Sparkle/PM3, a global minimum for the geometry of a given complex, with the understanding that it will tend to be closer to the experimental geometry, appears to be warranted. Therefore, the sparkle model is seemingly a trustworthy semiempirical quantum chemical model for the prediction of lanthanide complexes geometries.

• 出版日期2007-8