Adsorption of diatomic molecules on iron tape-porphyrin: A comparative study
Adsorption of diatomic molecules on iron tape-porphyrin: A comparative study
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DOI：
10.1103/physrevb.77.195307
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发表时间：
2008-05
影响因子：
3.7
通讯作者：
T. Nguyen;M. C. Escaño;Nobuaki Shimoji;H. Nakanishi;H. Kasai
中科院分区：
文献类型：
--
作者：
T. Nguyen;M. C. Escaño;Nobuaki Shimoji;H. Nakanishi;H. Kasai
我们使用基于密度泛函理论的第一原理计算研究了双原子分子、CO、NO 和铁带卟啉 (FeTP) 的吸附。在这项工作中，我们展示了铁带卟啉及其与 CO、NO 和的配合物的结构和电子性质。这种双原子分子与 FeTP 的结合引起了 FeTP 的几何结构和电子性质的显着变化。我们发现，在所有具有双原子分子的 FeTP 配合物中，Fe 原子从卟啉平面移向吸附的分子。铁-双原子分子键的能量按Fe-O2(0.554eV)<Fe-CO(1.225eV)<Fe-NO(1.719eV)的顺序增加。在其稳定位置，角度按 的顺序增加。几何结构的变化与卟啉分子的其他密度泛函理论计算和实验结果一致。至于电子性质，在CO吸附和NO吸附情况下，导带和价带之间出现了能隙，其中前者的能隙更明显，而在吸附情况下没有观察到能隙。我们将电子特性的这些变化归因于涉及铁原子轨道和双原子分子轨道的强相互作用。具体来说，对于吸附在 FeTP 上的 CO 和 NO，电子性质的变化归因于 Fe 原子和轨道的强杂化。对于吸附在 FeTP 上，Fe 原子轨道与轨道的杂化在铁带-卟啉相互作用中起着关键作用。
We investigated the adsorption of diatomic molecules, CO, NO, and, denoted byon iron tape-porphyrin (FeTP) using first-principles calculations based on density functional theory. In this work, we present the structure and electronic properties of iron tape-porphyrin and its complexes with CO, NO, and. The binding of such diatomic molecules to FeTP gave rise to significant changes on both the geometric structure and electronic properties of FeTP. We found that in all FeTP complexes with diatomic molecules, the Fe atom moves out of the porphyrin plane toward the adsorbed molecule. The energy of the iron-diatomic molecule bond increases in the order of Fe-O2(0.554eV)<Fe-CO(1.225eV)<Fe-NO(1.719eV). At its stable position, theangle increases in the order of. The changes in geometric structure are in accordance with other density functional theory calculations and experimental results for porphyrin molecule. As regards the electronic properties, there appears an energy gap between the conduction band and valence band in CO-adsorbed and NO-adsorbed cases with a more pronounced energy gap in the former, while none was observed in the-adsorbed case. We attribute these changes in electronic properties to the strong interaction involving theorbitals of the Fe atom and theorbitals of diatomic molecules. Specifically, for the CO and NO adsorbed on FeTP cases, the change in electronic properties is attributed to the strong hybridization ofandorbitals of the Fe atom andorbitals. Foradsorbed on FeTP, the hybridization of theorbital of the Fe atom andorbitals plays the key role in–iron tape-porphyrin interaction.