The band structure of porphyrinatonickel (II). A semiempirical crystal orbital study based on the tight-binding formalism
The band structure of porphyrinatonickel (II). A semiempirical crystal orbital study based on the tight-binding formalism
复制标题
卟啉镍 (II) 的能带结构。
DOI：
10.1002/qua.560250506
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发表时间：
1984
影响因子：
2.2
通讯作者：
M. Böhm
中科院分区：
文献类型：
--
作者：
M. Böhm
The band structure of porphyrinatonickel(II) (2) has been studied by means of crystal orbital calculations that are based on the tight-binding approximation; the computational framework is a recently developed INDO model for transition metal compounds of the 3d series. The porphyrinato polymer has been studied in an eclipsed arrangement (2a) and in a staggered conformation (2b) where neighboring layers are rotated by 41°. The total energy of the metallomacrocycle has been decomposed into one- and two-center contributions; the latter interaction parameters have been fragmented into physically feasible resonance, exchange, and classical electrostatic (electron–electron, electron–core, core–core) interactions. It is shown that individual two-center potentials between atoms in neighboring layers are prevailingly determined by the electrostatic interaction energy. The NiNi coupling in the chain is highly repulsive; important stabilizing interactions are predicted between the 3d center of one cell and the electronegative N atoms in the neighboring layers. Stabilizing and destabilizing electrostatic interaction potentials largely compensate each other; the net stabilization in the polymer comes from the accumulation of resonance and exchange increments. The unoxidized Ni(II) porphyrinato polymer is an insulator. Several ligand bands (π, σ, and lone-pair) are predicted on top of bands with significant Ni 3d admixtures; the conduction band of the unoxidized strand is of ligand π* character. The dense manifold of ligand states in the vicinity of the Ni 3d states (3d, 3d, 3dxz/3dyz) prevents the formation of bands in the polymer that are strongly localized at the 3d center. Ni 3d and 3d interact strongly with ligand lone-pair and σ states. Avoided crossings between ϵ(k) curves in k space lead to compositions in the various bands that differ significantly at the bottom and the top. The INDO crystal orbital formalism predicts a partial oxidation of ligand bands in derivatives of 2 that contain oxidants (e.g., halides). The theoretical findings derived for 2 are compared with available experimental data on highly conducting porphyrinatonicke(II) polymers (tetrabenzo and octamethyltetrabenzo derivatives of 2).
