两个组件的相对论运动方程合集群用于电子电离
Stephen H Yuwono1, Run R Li1, Tianyuan Zhang2
1Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA.
The Journal of chemical physics
|February 26, 2025
概括
我们开发了一种相对论计算方法,用于准确的电离潜力和分子中的自旋轨道分裂. 这种方法使用3孔2粒子激发,准确地预测了化乙酸盐的这些特性.
科学领域:
- 计算化学计算化学
- 量子化学 是一个量子化学.
- 相对论量子力学相对论量子力学
背景情况:
- 准确预测分子电子特性,特别是旋转轨道分裂,对于理解化学行为至关重要.
- 对于较重的元素,相对论效应变得显著,需要专门的计算框架.
- 现有的方法可能会与退化作斗争,或需要计算上昂贵的开放系统的不受限制的引用.
研究的目的:
- 实施和验证一种相对论的电离电位运动方程合集群 (IP-EOMCC) 方法,该方法包含多达3孔2粒子 (3h2p) 激发.
- 为了利用精确的两组件 (X2C) 框架和迪拉克-库伦布-布莱特哈密尔顿式,以获得高精度.
- 准确预测开分子中的自旋轨道分裂和电离潜力,而不会破坏空间对称性.
主要方法:
- 开发使用3h2p激发的X2C-IP-EOMCC方法.
- 使用封闭外的参考状态,以避免在开放外计算中发生退化破坏.
- 使用大型基数集 (四倍泽塔质量) 对HCCX+ (X = Cl, Br, I) 离子的基态和兴奋状态的应用.
主要成果:
- 使用3h2p激发的X2C-IP-EOMCC方法提供了准确的离电离电位 (IPs),最大误差为~0.1 eV.
- 计算的旋转轨道分裂与实验值非常一致,精度约为0.01 eV.
- 大基数组和3h2p相关性效应对于实现绝对能量学高精度至关重要.
结论:
- 实施的相对论X2C-IP-EOMCC方法对于预测电离潜力和旋转轨道分裂非常有效.
- 在这个框架中使用封闭外参考状态可以避免在开放外系统中发生退化断裂的问题.
- 这种计算方法为研究含有重原子的分子的相对论效应和电子性质提供了可靠的工具.
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