系统研究硬墙封闭对原子电子结构产生的影响
1Department of Chemistry, Faculty of Science, University of Helsinki, P.O. Box 55, A.I. Virtanens Plats 1, University of Helsinki FI-00014, Finland.
The journal of physical chemistry. A
|January 29, 2025
概括
这项研究系统地使用先进的数值方法研究被硬墙所限制的原子. 结果显示,在封闭状态下,显著的电子转移和原子配置的变化影响了电离半径和范德瓦尔斯半径的预测.
科学领域:
- 计算物理和化学计算物理和化学
- 量子力学就是量子力学.
- 原子物理 原子物理
背景情况:
- 现有的关于受限原子的研究缺乏系统的方法和强大的数值方法.
- 对于各种物理和化学现象来说,了解被封闭的原子行为至关重要.
研究的目的:
- 进行原子 (H-Xe) 和它们的单离子在硬墙封闭中的方法研究.
- 为了研究受限对原子配置,电子分布和电离半径的影响.
- 评估和建议改进基于密度的范德瓦尔斯半径估计.
主要方法:
- 使用了HelFEM程序,使用有限元法来准确地实现硬墙潜力.
- 执行了非相对论密度函数理论计算,使用三个近似值:PW92,PBE和r2SCAN.
- 对于低层配置的计算属性,包括旋转极化和旋转受限制的密度,跨越不同的限制边界.
主要成果:
- 密度函数近似显示出很好的一致性,这表明独立于所选函数的可靠发现.
- 观测到显著的电子移位,其中价值 s 电子受到不利影响,高层 d 和 f 轨道在强烈的限制下被占据.
- 与以前的研究相比,计算的电离辐射显示出了实质性的差异,突出了封闭效应的重要性.
结论:
- 系统的数值计算证实了由于硬壁封闭而导致的原子结构和电子性质的显著变化.
- 旋转极化效应对于封闭原子中的开放外配置至关重要.
- 为范德瓦尔斯半径提出了基于密度的精细估计,解决了当前模型中的缺陷.
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