Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
Inorg Chem. 2011 Oct 17;50(20):10259-67. doi: 10.1021/ic2013107. Epub 2011 Sep 16.
We introduce a novel theoretical approach for determining oxidation states (OS) from quantum-mechanical calculations. For a transition-metal ion, for example, the metal-ligand orbital mixing contribution to the charge allocated to the ion is separated from that due to the actual occupation of the d-orbitals from which OS can then be inferred. We report the application of this approach to different transition-metal systems: molecular complexes, ruthenium-dye molecules, ruthenium complexes with noninnocent ligands, and bulk semiconductors. The computations were carried out using density-functional theory with a Hubbard U correction. The oxidation states were determined without ambiguity.
我们提出了一种从量子力学计算中确定氧化态（OS）的新理论方法。例如，对于过渡金属离子，可以将配体轨道混合对离子分配电荷的贡献与由于实际占据 d 轨道而导致的贡献区分开来，然后可以推断出 OS。我们报告了该方法在不同过渡金属系统中的应用：分子配合物、钌染料分子、具有非中性配体的钌配合物和体半导体。计算是使用带有 Hubbard U 校正的密度泛函理论进行的。氧化态的确定没有歧义。
