对于开系统的Kohn-Sham反转
Jannis Erhard1, Egor Trushin1,2, Andreas Görling1,2
1Lehrstuhl für Theoretische Chemie, Universität Erlangen-Nürnberg, Egerlandstr. 3, D-91058 Erlangen, Germany.
The Journal of chemical physics
|January 16, 2025
概括
密度函数理论方法通常会打破对称性,导致诸如旋转污染等问题. 本研究引入了稳定的方法来构建Kohn-Sham潜力,恢复对称性并为开系统提供参考能量值.
科学领域:
- 量子化学 是一个量子化学.
- 计算物理 计算物理
- 材料科学 材料科学 材料科学
背景情况:
- 标准密度函数理论 (DFT) 方法使用自旋不受限制的Kohn-Sham (KS) 形式主义用于开放系统.
- 这种方法打破了空间和旋转对称性,导致旋转污染,并阻碍了适当的波函数分类.
- 存在恢复对称性的KS变体,但很少实施.
研究的目的:
- 开发数值稳定的Kohn-Sham (KS) 倒置方法,从参考旋转密度中构建KS潜力.
- 研究四种对称性对待开放系统的方法:非对称,旋转对称,空间对称和完全对称.
- 为跨越这些形式主义的能量成分差异提供参考值.
主要方法:
- 采用了数量稳定的KS反转技术.
- 从参考旋转密度构建的参考KS潜力.
- 使用完整配置相互作用和对原子和二原子分子的合集群方法获得的参考旋转密度.
主要成果:
- 成功构建了所有四种对称性治疗的KS潜力.
- 证明了能量分解在四个KS形式上有所不同.
- 确定非完全对称的KS反向可以违反 Aufbau 原则,并且在旋转对称的情况下,KS v-可表示性.
结论:
- 该研究为应用对称性恢复KS形式主义提供了实际框架.
- 参考能量值是为了比较不同的对称性处理而建立的.
- 违反物理原则,如 Aufbau 原则和 KS v 代表性,突出了完全对称的方法的重要性.
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