一种相对论配置交互方法,具有对电子g因子的一般扩展和初始应用
1Department of Chemistry, Aarhus University, Langelandsgade 140, DK 8000 Aarhus C, Denmark.
The Journal of chemical physics
|July 24, 2023
概括
一种新的计算方法准确地计算了二元原子基的电子g转移,如AlO,HgF和PdH. 这种方法有效地处理复杂的电子相互作用,实现价值电子的融合,但面临核心电子激发的挑战.
科学领域:
- 计算化学的计算化学
- 量子化学 是一个量子化学.
- 相对论的计算 相对论的计算
背景情况:
- 精确计算电子g转移对于理解分子性质至关重要.
- 对于重元素,相对论效应变得显著,需要先进的计算方法.
- 配置交互 (CI) 方法很强大,但计算要求很高.
研究的目的:
- 报告基于轨道的双组件相对论配置相互作用 (CI) 方法的新实现.
- 应用这种新方法来计算二元原子基AlO,HgF和PdH的电子g转移.
- 为了研究电子g-shift的收性质与活性空间大小,轨道优化和激发水平的关系.
主要方法:
- 开发了一种新的两部分相对论 CI 方法的实施方法.
- 增强了现有的例行程序,用于旋转轨道运算符的向量化计算.
- 利用双组和时间逆转对称,以及粒子孔重组以提高效率.
主要成果:
- 新的实现允许对一般化的活跃空间扩张进行高效的计算.
- 计算了AlO,HgF和PdH的电子g转移.
- 通过多达四倍激发,可以达到几百分之内对价值极限的收,但在测试的决定性空间内对核心轨道激发无法证明收.
结论:
- 新的相对论CI实现是有效和灵活的研究电子g-shifts.
- 该研究强调了包括足够激发对于准确的g-shift计算的重要性.
- 在核心轨道激发显著时,需要进一步开发以实现收的结果.
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