精确的F12电子结构模型的更苗条的双胞胎
Samuel R Powell1, Kshitijkumar A Surjuse1, Bimal Gaudel1
1Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24060, United States.
Journal of chemical theory and computation
|September 10, 2025
概括
新的双元参数通过减少基础集不完整性误差 (BSIE) 来改进高阶F12方法. 这种优化增强了结合集群F12计算中的相关性能量,特别是在专门的基础集合中.
科学领域:
- 量子化学 是一个量子化学.
- 计算化学计算化学
- 理论化学 理论化学
背景情况:
- 斯莱特型双长度尺度对于F12方法至关重要.
- 现有的参数优化为第二阶的Møller-Plesset F12不适合更高阶的F12方法.
研究的目的:
- 开发和报告高阶F12方法的新双质参数.
- 为了减少相关的能源计算中的基础设置不完整性错误 (BSIE).
主要方法:
- 对F12方法的双重参数进行重新优化.
- 在结合集群单项和双项F12 (CCSD(2) -F12计算中的应用.
- 与传统和F12优化的基础集 (例如cc-pVXZ-F12) 的比较.
主要成果:
- 新的参数显著降低了绝对关联能量的BSIE.
- 这种改善在基础集合中较大的枢机数时更为明显.
- 对于相对能量,特别是原子化能量和电离潜力,BSIE的实质性减少被观察到.
结论:
- 对于高阶F12方法,重新优化的双质参数是推的.
- 这包括结合集群F12和跨相关F12方法.
- 这些发现提高了使用F12技术进行量子化学计算的准确性.
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