Electronic Structure, Spin-States, and Spin-Crossover Reaction of Heme-Related Fe-Porphyrins: A Theoretical Perspective

被引:102
作者
Ali, Md. Ehesan [1 ]
Sanyal, Biplab [2 ]
Oppeneer, Peter M. [2 ]
机构
[1] Ruhr Univ Bochum, Ctr Theoret Chem, D-44780 Bochum, Germany
[2] Uppsala Univ, Dept Phys & Astron, S-75120 Uppsala, Sweden
基金
瑞典研究理事会;
关键词
IRON-OXYGEN BOND; TRANSITION-METAL; DENSITY FUNCTIONALS; MAGNETIC-PROPERTIES; THERMOCHEMICAL KINETICS; CO; COMPLEXES; O-2; INTERMEDIATE; ENERGETICS;
D O I
10.1021/jp3021563
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
The electronic structures, spin-states, and geometrical parameters of tetra-, penta-, and hexa-coordinated iron-porphyrins are investigated applying density functional theory (DFT) based calculations, utilizing the plane-wave pseudopotential as well as localized basis set approaches. The splitting of the spin multiplet energies are investigated applying various functionals including recently developed hybrid meta-GGA (M06 family) functionals. Almost all of the hybrid functionals accurately reproduce the experimental ground state spins of the investigated Fe-porphyrins. However, the energetic ordering of the spin-states and the energies between them are still an issue. The widely used B3LYP provides consistent results for all chosen systems. The GGA+U functionals are found to be equally competent. After assessing the performance of various functionals in spin-state calculations, the potential energy surfaces of the oxygen binding process by heme is investigated. This reveals a "double spin-crossover" feature for the lowest energy reaction path that is consistent with previous CASPT2 calculations but predicting a lowest energy singlet state. The calculations have hence captured the spin-crossover as well as spin-flip processes. These are driven by the intra-atomic orbital polarization on the central metal atom due to the atomic and orbitals rearrangements. The nature of the chemical bonding and a molecular orbital analysis are also performed for the geometrically simple but electronic structurally complicated system tetra-coordinated planar Fe porphyrin in comparison to the penta-coordinated systems. This analysis explains the observed paradoxical appearance of certain peaks in the local density of states (DOS).
引用
收藏
页码:5849 / 5859
页数:11
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