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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structure and spectroscopic properties of iron oxides with the high content of oxygen: FeO_n and FeO_n (n = 512)
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Structure and spectroscopic properties of iron oxides with the high content of oxygen: FeO_n and FeO_n (n = 512)

机译:高氧含量的铁氧化物:FeO_n和FeO_n(n = 512)的结构和光谱性质

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摘要

The electronic and geometrical structures of oxygen-rich neutral and negatively charged FeO_5, FeO_6, FeO_7, FeO _8, FeO_9, FeO_(10), FeO_(11), and FeO _(12) clusters were obtained using density functional theory with generalized gradient approximation. With the exception of FeO_(11) and FeO_(12), all clusters are found to possess a large number of isomers composed of oxo, peroxo, superoxo, and ozonide fragments that are closely spaced in total energy, especially for n = 7 and 8. The preferable structures of FeO_(12) are composed of superoxo groups with different orientations. All the neutral species possess rather large electron affinities, which range from 3.24 eV (FeO_8) to 3.95 eV (FeO_5). Although all of the lowest energy states were found to possess positive vibrational frequencies and thus are geometrically stable, the states are thermodynamically unstable against dissociation to FeO_4 + (n 4)/2 O_2 for n = 6, 8, 10, and 12 and FeO_5 + (n 5)/2 O_2 for n = 7, 9, and 11. In particular, the decay of FeO_(12) is exothermic by 34 kcal/mol.
机译:使用具有广义梯度的密度泛函理论获得富氧的中性和负电荷的FeO_5,FeO_6,FeO_7,FeO_8,FeO_9,FeO_(10),FeO_(11)和FeO __(12)团簇的电子和几何结构近似。除FeO_(11)和FeO_(12)外,发现所有簇都具有大量的异构体,这些异构体由oxo,peroxo,superoxo和ozonide片段组成,它们的总能量非常接近,尤其是对于n = 7和8. FeO_(12)的优选结构由具有不同方向的超氧代基团组成。所有中性物质都具有相当大的电子亲和力,范围从3.24 eV(FeO_8)到3.95 eV(FeO_5)。尽管发现所有最低能量状态都具有正振动频率,因此在几何上是稳定的,但对于n = 6、8、10和12和FeO_5,这些状态对于解离为FeO_4 +(n 4)/ 2 O_2而言是热力学不稳定的。 +(n 5)/ 2 O_2,其中n = 7、9和11。特别是,FeO_(12)的衰减以34 kcal / mol放热。

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