Theoretical study of the electronic ground state of iron(II) porphine. II
Theoretical study of the electronic ground state of iron(II) porphine. II
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DOI：
10.1063/1.479687
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发表时间：
1999-09-01
影响因子：
4.4
通讯作者：
Lindh, R
中科院分区：
文献类型：
--
作者：
Choe, YK;Nakajima, T;Lindh, R
Fe（Ⅱ）卟啉的十个低电子态，（5）A（1g），E-5（g），B-5（2g），（3）A（2g），B-3（2g），E-3（g）（A），E-3（g）（B），（1）A（1g），B-1（2g），E-1（g）态，采用完全活性空间自洽场（CASSCF）的多组态二阶微扰（CASPT 2）计算方法，具有更大有效空间和基集的参考函数。活动空间和基组的扩大没有影响以前的多参考Moller-Plesset微扰（MRMP）研究的结论。目前的CASPT 2计算得出结论，（5）A（1g）态是基态。用相对论性消去小分量方案（RESC）作了相对论性修正。在能量学方面，相对论修正没有显著的贡献，相对能和轨道能没有明显的变化。目前的结果并不同意所有的光谱观测，但与磁矩的研究是一致的。(C)1999年美国物理学会。[S0021-9606（99）30233-6]。
Ten low-lying electronic states of Fe(II) porphine, (5)A(1g), E-5(g), B-5(2g), (3)A(2g), B-3(2g), E-3(g)(A), E-3(g)(B), (1)A(1g), B-1(2g), and E-1(g) states, are studied with multiconfigurational second-order perturbation (CASPT2) calculations with complete active space self-consistent field (CASSCF) reference functions with larger active space and basis sets. The enlargement of active space and basis sets has no influence on the conclusion of a previous multireference Moller-Plesset perturbation (MRMP) study. The present CASPT2 calculation concludes that the (5)A(1g) state is the ground state. A relativistic correction has been performed by the relativistic scheme of eliminating small components (RESC). For energetics, no significant contribution from the relativistic correction was found. The relative energies and orbital energies are not changed appreciably by the introduction of a relativistic correction. The present result does not agree with all the spectroscopic observations, but is consistent with a magnetic moment study. (C) 1999 American Institute of Physics. [S0021-9606(99)30233-6].