激发状态静态极化:CC3参考值,波函数和TD-DFT基准值
Carmelo Naim1, Robert Zaleśny2, Denis Jacquemin1,3
1Nantes Université, CNRS, CEISAM UMR 6230, Nantes F-44000, France.
Journal of chemical theory and computation
|February 12, 2026
概括
这项研究对有机分子的兴奋状态极化性进行了基准测试. 像CCSD和CC2这样的合集群方法提供了最准确的结果,CC2是计算效率高的替代方案.
科学领域:
- 计算化学的计算化学
- 量子化学 是一个量子化学.
- 分子建模分子建模
背景情况:
- 激发状态的极化对于理解分子对电场的反应至关重要.
- 准确的理论数据是必要的比较计算方法.
研究的目的:
- 为了对各种计算方法进行基准测试,用于计算激发状态极化性.
- 评估基于波函数的方法和时间依赖密度函数理论 (TD-DFT) 的性能.
主要方法:
- 高级合集群CC3计算使用aug-cc-pVTZ基准设置作为参考数据.
- 与CCSD,CC2和几个TD-DFT函数 (B3LYP,MN15,M06-2X,CAM-B3LYP,LC-BLYP) 相比进行基准测试.
- 对价值状态和Rydberg状态的分析,考虑轨道放松效应.
主要成果:
- CCSD和CC2方法提供高度准确的兴奋状态极化性.
- CC2是一种可靠且计算效率高的替代方案.
- 在TD-DFT函数中,范围分离混合体 (LC-BLYP) 的表现最好,而全局混合体显示更大的错误.
结论:
- 建议使用CCSD和CC2来准确计算激发状态的极化性.
- CC2提供了精度和计算成本的实用平衡.
- 根据功能选择,TD-DFT的性能有很大差异,范围分离的混合动力是优越的.
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