Simulation of 59Co NMR chemical shifts in aqueous solution

被引：56

作者：

Bühl, M ^{[1
]}

Grigoleit, S ^{[1
]}

Kabrede, H ^{[1
]}

Mauschick, FT ^{[1
]}

机构：

[1] Max Planck Inst Kohlenforsch, D-45470 Mulheim, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2006年 / 12卷 / 02期

关键词：

density functional calculations; molecular dynamics; NMR spectroscopy; solvation effects; transition metals;

D O I：

10.1002/chem.200500285

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Co-59 chemical shifts were computed at the GIAO-B3LYP level for [Co(CN)(6)](3-), [Co(H2O)(6)](3+), [Co- (NH3)(6)](3+), and [Co(CO)(4)](-) in water. The aqueous solutions were modeled by Car-Parrinello molecular dynamics (CPMD) simulations, or by propagation on a hybrid quantum-mechanical/ molecular-mechanical Born-Oppenheimer surface (QM/MM-BOMD). Mean absolute deviations from experiment obtained with these methods are on the order of 400 and 600 ppm, respectively, over a total delta(Co-59) range of about 18000 ppm. The effect of the solvent on delta(Co-59) is mostly indirect, resulting primarily from substantial Metal-ligand bond contractions on going from the gas phase to the bulk. The simulated solvent effects on geometries and delta(Co-59) values are well reproduced by using a polarizable continuum model (PCM), based on optimization and perturbational evaluation of quantum-mechanical zero-point corrections.

引用

页码：477 / 488

页数：12

共 104 条

[91] Structure and dynamics of metal ions in solution:: QM/MM molecular dynamics simulations of Mn2+ and V2+ [J].