三维和四维过渡金属的地面和激发状态:对原子性质的计算洞察力
Ebtisam M Z Telb1, Nuno M S Almeida1, Bradley K Welch1
1Department of Chemistry, Michigan State University, East Lansing, Michigan 48864, United States.
The journal of physical chemistry. A
|September 22, 2025
概括
预测过渡金属的电子状态是一项挑战. 超相关性一致的复合方法 (s-ccCA) 显示了这些复杂的原子系统与实验值的最小偏差.
科学领域:
- 量子化学 是一个量子化学.
- 原子物理 原子物理
- 计算化学计算化学
背景情况:
- 对3D和4D过渡金属的电子状态的计算预测是复杂的,原因是高状态密度,多个旋转和狭窄的能量差距.
- 准确计算地面和低兴奋状态对于理解过渡金属特性至关重要.
研究的目的:
- 研究和比较各种计算方法的准确性,用于预测第一和第二排过渡金属原子的能量多元体.
- 分析不同理论选择,包括基础集和标量相对论效应对能源预测的影响.
主要方法:
- 采用超相关性一致的复合方法 (s-ccCA) 和几种多引用波函数方法.
- 使用了相关联一致的基础集,并纳入了标量相对论效应.
- 将结果推算到完整的基础设置极限,以提高准确性.
主要成果:
- 与戴维森校正 (MRCI+Q) 进行的多参考配置交互证明了大多数过渡金属原子的高可靠性和精度.
- 与实验数据相比,超相关性一致的复合方法 (s-ccCA) 显示出最小的偏差.
- 分析显示,所选择的方法和基础对能源预测准确性的重大影响.
结论:
- s-ccCA 方法为计算过渡金属原子的电子状态提供了一个高度准确和可靠的方法.
- 虽然MRCI+Q是一种强大的方法,但s-ccCA与实验结果具有更高的一致性.
- 仔细选择计算方法和基础集对于过渡金属化学中的准确预测至关重要.
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