Spin state and magnetic coupling in polynuclear Ni(II) complexes from density functional theory: is there an optimal amount of Fock exchange?

被引:2
作者
Manukovsky, Nurit [1 ,3 ]
Kamieniarz, Grzegorz [2 ]
Kronik, Leeor [1 ]
机构
[1] Weizmann Inst Sci, Dept Mol Chem & Mat Sci, IL-7610001 Rehovot, Israel
[2] Adam Mickiewicz Univ, Fac Phys, PL-61614 Poznan, Poland
[3] Tel Aviv Univ, Sch Chem, IL-6997801 Tel Aviv, Israel
关键词
TRANSITION-METAL-COMPLEXES; RANGE-SEPARATED HYBRID; ELECTRONIC-STRUCTURE; SELF-INTERACTION; AB-INITIO; IRON; ENERGETICS; CROSSOVER; TEMPERATURE; ENERGY;
D O I
10.1063/5.0169105
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
Reliable prediction of the ground-state spin and magnetic coupling constants in transition-metal complexes is a well-known challenge for density functional theory (DFT). One popular strategy for addressing this long-standing issue involves the modification of the fraction of Fock exchange in a hybrid functional. Here we explore the viability of this approach using three polynuclear metal-organic complexes based on a Ni4O4 cubane motif, having different ground state spin values (S = 0, 2, 4) owing to the use of different ligands. We systematically search for an optimum fraction of Fock exchange, across various global, range-separated, and double hybrid functionals. We find that for all functionals tested, at best there only exists a very narrow range of Fock exchange fractions which results in a correct prediction of the ground-state spin for all three complexes. The useful range is functional dependent, but general trends can be identified. Typically, at least two similar systems must be used in order to determine both an upper and lower limit of the optimal range. This is likely owing to conflicting demands of minimizing delocalization errors, which typically requires a higher percentage of Fock exchange, and addressing static correlation, which typically requires a lower one. Furthermore, we find that within the optimal range of Fock exchange, the sign and relative magnitude of Ni-Ni magnetic coupling constants are reasonably well reproduced, but there is still room for quantitative improvement in the prediction. Thus, the prediction of spin state and magnetic coupling in polynuclear complexes remains an ongoing challenge for DFT.
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页数:9
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