电子结构和稳定性Trimethylsilyl-Masked基和基复合离子和对它们的化物进行比较:一组合光电子光谱和计算研究
Wenjin Cao1, Xiao-Fei Gao1, Kevin Dollberg2
1Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.
Inorganic chemistry
|March 17, 2026
概括
这项研究揭示了三甲基 (triMS) 蒙面的基和基离子表现出增强的电子稳定性. 旋转轨道合对于理解这些系统中较重的元素至关重要.
科学领域:
- 无机化学 无机化学
- 计算化学的计算化学
- 频谱学是一种光谱学.
背景情况:
- 基 (Pn) 和基 (Ch) 离子是化学中的基本元素.
- 了解它们的电子结构和稳定性是设计新材料和反应的关键.
- 三甲基基 (triMS) 组提供了一种稳定这些离子的新方法.
研究的目的:
- 为了研究triMS-masked pnictogen (Pn(triMS) 2-) 和 chalcogen (Ch(triMS) - - 离子的电子结构和稳定性.
- 为了确定这些新离子的精确的离和垂直脱离能量 (ADE和VDE).
- 阐明旋转轨道合 (SOC) 在较重的平基和基离子的电子性质中的作用.
主要方法:
- 负离子光电子光谱学被用来探测电子状态.
- 进行了量子化学计算,包括使用SOC进行相对论多参考计算.
- 将光谱数据与理论计算进行比较,可以进行详细分析.
主要成果:
- 在Pn和C anion系列之间观察到明显的电子结构模式.
- 与化物类似物相比,Pn ((triMS) 2 - 和Ch ((triMS) - 的ADE和VDE值大得多,这表明稳定性提高.
- 在Pn和Ch两组中,从较轻的元素到较重的元素,ADE增加的下降趋势被注意到.
- 包括SOC在内的相对论计算对于准确地复制更重元素的光谱配置文件至关重要.
结论:
- TriMS 掩盖增强了 pnictogen 和 chalcogen 离子的电子稳定性.
- 电子性质和稳定性趋势受到单双电子和triMS连接体数量的影响.
- 旋转轨道合在较重的平基和基系统的电子结构中起着关键作用,因此需要将其纳入理论模型.
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