Electronic structure and bonding in metal porphyrins, metal=Fe, Co, Ni, Cu, Zn
Electronic structure and bonding in metal porphyrins, metal=Fe, Co, Ni, Cu, Zn
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DOI：
10.1063/1.1480872
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发表时间：
2002-07-01
影响因子：
4.4
通讯作者：
Scheiner, S
中科院分区：
文献类型：
--
作者：
Liao, MS;Scheiner, S
用密度泛函理论方法对金属meso-四苯基卟啉MTPP（M=Fe，Co，Ni，Cu，Zn）的电子结构和成键进行了系统的理论研究.计算提供了MTPP和一系列[MTPP]（x）离子（x=2+，1+，1-，2-，3-，4-）的基态的清晰说明，这有助于理解许多观察到的电子性质。计算支持未连接的FeTPP的实验归属为（3）A（2g），其源自构型（d（xy））（2）（d（z）（2））（2）（d（xz））（1）（d（yz））（1）。计算的M-TPP的结合能，电离势，和电子亲合能与现有的实验数据吻合得很好。轴向配体和外围氟取代的影响与实验观察结果雅阁，即卟啉的碱性和轴向配体的配位类型不仅决定了电极反应的半波电位（E-1/2），而且也决定了氧化/还原的位置。(C)2002年美国物理学会。
A systematic theoretical study of the electronic structure and bonding in metal meso-tetraphenyl porphines MTPP, M=Fe, Co, Ni, Cu, Zn has been carried out using a density functional theory method. The calculations provide a clear elucidation of the ground states for the MTPPs and for a series of [MTPP](x) ions (x=2+, 1+, 1-, 2-, 3-, 4-), which aids in understanding a number of observed electronic properties. The calculation supports the experimental assignment of unligated FeTPP as (3)A(2g), which arises from the configuration (d(xy))(2)(d(z)(2))(2)(d(xz))(1)(d(yz))(1). The calculated M-TPP binding energies, ionization potentials, and electron affinities are in good agreement with available experimental data. The influence of axial ligands and peripheral substitution by fluorine are in accord with the experimental observation that not only half-wave potentials (E-1/2) of electrode reactions, but also the site of oxidation/reduction, may be dependent on the porphyrin basicity and the type of axial ligand coordination. (C) 2002 American Institute of Physics.