Accurate Modeling of Spin-State Energetics in Spin-Crossover Systems with Modern Density Functional Theory

被引：206

作者：

Ye, Shengfa ^{[1
]}

Neese, Frank ^{[1
]}

机构：

[1] Univ Bonn, Lehrstuhl Theoret Chem, Inst Phys & Theoret Chem, D-53115 Bonn, Germany

来源：

INORGANIC CHEMISTRY | 2010年 / 49卷 / 03期

关键词：

TRANSITION-METAL-COMPLEXES; SULFUR LIGANDS; AB-INITIO; PERTURBATION-THEORY; ENERGY; IRON; VALIDATION; REACTIVITY; MOLECULES; THIOETHER;

D O I：

10.1021/ic902365a

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The energies of different spin multiplicities of a range of iron complexes are computed using modern density functional theory (DFT) methods of the generalized gradient approximation (GGA; BP86 and OPBE), meta-GGA (TPSS), hybrid meta-GGA (TPSSh), hybrid (B3LYP), and double-hybrid (B2PLYP) types. It is shown that so far only the double-hybrid density functional B2PLYP, in conjunction with large and flexible basis sets (def2-QZVPP), is able to provide qualitatively correct results of spin-state energetics for the investigated non-spin-crossover complexes. An energy difference of -6 to 0 kcal/mol is proposed to be indicative of spin-crossover behavior.

引用

页码：772 / 774

页数：3

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