过渡金属化合物的自动化多参考垂直激发
Jacob J Wardzala1, Daniel S King1, Laura Gagliardi2
1Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
The journal of physical chemistry. A
|March 4, 2025
概括
本研究引入了一种自动化方法,用于在过渡金属复合体的电子结构计算中选择活性空间. 离散变量选择与近似对系数 (DVS-APC) 方法简化了复杂的计算,提高了准确性和效率.
科学领域:
- 计算化学计算化学
- 量子化学 是一个量子化学.
- 材料科学 材料科学 材料科学
背景情况:
- 过渡金属复合体的兴奋状态与近退化的d轨道有很强的相关性.
- 精确的电子结构计算需要多引用方法.
- 这些方法中的活跃空间选择具有挑战性,通常依赖于经验方法.
研究的目的:
- 开发和验证一种自动化方法,用于在过渡金属系统中选择活跃空间.
- 与传统方法相比,评估自动化方法的准确性.
- 调查在不牺牲准确性的情况下减少活动空间大小的潜力.
主要方法:
- 开发了离散变量选择与近似对系数 (DVS-APC) 方法.
- 对于轨道与离散变量选择 (DVS) 的联合近似对系数 (APC),以获得活动空间质量.
- 应用DVS-APC在过渡金属二氧化物和两个更大的复合体中的67个垂直激发.
主要成果:
- 在DVS-APC产生的活性空间中,对于过渡金属二氧化物,NEVPT2的平均绝对误差为0.18 eV.
- 这种精度可以与有机系统相提并论,但略低于手工选择的空间 (0.14 eV).
- 该方法证明了对下方样本波函数的能力,在较小的活性空间下保持精度.
结论:
- DVS-APC方法为过渡金属复合物的兴奋状态提供了强大的自动化方法来选择活跃空间.
- DVS和手动选择空间之间的偏差可能表明手动选择中的偏差.
- 在复杂的过渡金属系统中,DVS-APC显示出模拟激发状态的前景.
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