Can DFT Accurately Predict Spin Densities? Analysis of Discrepancies in Iron Nitrosyl Complexes

被引：94

作者：

Boguslawski, Katharina ^{[2
]}

Jacob, Christoph R. ^{[1
]}

Reiher, Markus ^{[2
]}

机构：

[1] Karlsruhe Inst Technol KIT, Ctr Funct Nanostruct, D-76131 Karlsruhe, Germany

[2] ETH, Phys Chem Lab, CH-8093 Zurich, Switzerland

来源：

JOURNAL OF CHEMICAL THEORY AND COMPUTATION | 2011年 / 7卷 / 09期

基金：

瑞士国家科学基金会;

关键词：

ELECTRONIC-STRUCTURE; AB-INITIO; FUNCTIONAL THEORY; STATE ENERGETICS; CIRCULAR-DICHROISM; CORRELATION-ENERGY; CROSSOVER COMPLEX; METAL-COMPLEXES; NO COMPLEXES; COMPOUND I;

D O I：

10.1021/ct1006218

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Iron nitrosyl complexes are a particularly challenging case for density functional theory. In particular, for the low-spin state, different exchange correlation functionals yield very different spin densities [Conradie, J.; Ghosh, A. J. Phys. Chem. B 2007, 111, 12621-12624]. Here, we investigate the origin of these differences in detail by analyzing the Kohn-Sham molecular orbitals. Furthermore, to decide which exchange correlation functionals yield the most accurate spin densities, we make comparisons to CASSCF calculations. To ensure that the spin densities are converged with respect to the size of the active space, this comparison is performed for [Fe(NO)](2+) as a model system. We find that none of the investigated exchange-correlation functionals are able to reproduce the CASSCF spin densities accurately.

引用

页码：2740 / 2752

页数：13

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