Hirva Pipsa, Haukka Matti, Jakonen Minna, Moreno M Andreina
Department of Chemistry, University of Joensuu, P.O. Box 111, FI-80101, Joensuu, Finland.
J Mol Model. 2008 Mar;14(3):171-81. doi: 10.1007/s00894-007-0259-7. Epub 2008 Jan 5.
The applicability of several popular density functionals in predicting the geometrical parameters and energetics of transition metal carbonyl complexes of iron, ruthenium and osmium has been studied. The methods tested include pure GGA functionals (BLYP, BP86, OPBE, HCTH, PBE, VSXC) and hybrid GGA functionals (B3PW91, B3LYP, PBE1PBE, MPW1K, B97-2, B1B95, PBE1KCIS). The effect of changing the metal basis set from Huzinaga's all-electron basis to SDD scECP basis was also studied. The results show, that hybrid functionals are needed in order to describe the back-bonding ability of the carbonyl ligands as well as to deal with metal-metal bonds. The best general performance, when also the computational cost was considered, was obtained with hybrid functionals B3PW91 and PBE1PBE, which therefore provide an efficient tool for solving problems involving large or medium sized transition metal carbonyl compounds.
研究了几种常用密度泛函在预测铁、钌和锇的过渡金属羰基配合物的几何参数和能量学方面的适用性。所测试的方法包括纯广义梯度近似（GGA）泛函（BLYP、BP86、OPBE、HCTH、PBE、VSXC）和杂化GGA泛函（B3PW91、B3LYP、PBE1PBE、MPW1K、B97-2、B1B95、PBE1KCIS）。还研究了将金属基组从胡齐纳加全电子基组改为SDD赝势基组的影响。结果表明，需要杂化泛函来描述羰基配体的反馈键合能力以及处理金属-金属键。考虑到计算成本，杂化泛函B3PW91和PBE1PBE表现出最佳的综合性能，因此为解决涉及大中型过渡金属羰基化合物的问题提供了一种有效的工具。
