在化中从离子到共价键的突然变化,伴随着联结体场反转
Max Flach1,2, Konstantin Hirsch1, Tim Gitzinger2
1Abteilung für Hochempfindliche Röntgenspektroskopie, Helmholtz-Zentrum Berlin für Materialien and Energie, Berlin 12489, Germany.
Inorganic chemistry
|June 10, 2024
概括
化离子的电子结构表明化是离子的,而较重的化是共价的. 这种差异影响了它们在催化过程中对氧化还原反应的潜力.
科学领域:
- 无机化学 无机化学
- 物理化学 物理化学
- 计算化学的计算化学
背景情况:
- 过渡金属和连接体的电子配置是理解氧化还原反应的关键.
- 单化离子在催化和电化学中很重要.
- 描述它们的电子结构为我们提供了关于结合和反应性的见解.
研究的目的:
- 为了确定气相单化离子的电子结构.
- 为了研究这些物种的结合性质 (离子与共价).
- 为了将电子结构与基于联结体的氧化还原反应的潜力相关联.
主要方法:
- 使用了L2,3-边缘X射线吸收光谱 (XAS).
- 实验频谱与多重电荷转移模拟进行了比较.
- 分析了单聚的基态和兴奋态配置.
主要成果:
- [NiF]+主要表现出与经典联结体场的离子结合.
- [NiCl]+,[NiBr]+和[NiI]+呈现出不断增加的共价贡献和一个反转的连接体场.
- 较重的化物具有3d9 L̲的配置,表明一个连接体孔和 () 特性.
- 在[NiF]+中没有连接体孔,可以防止基于连接体的氧化还原反应.
结论:
- 单化中的结合从离子转变为共价,随着化大小的增加.
- 电子结构决定了氧化还原活性的潜力,较重的化物更容易受到影响.
- 了解这些电子性质对于设计催化剂和电化学系统至关重要.
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