来自结合集群响应理论的源自独立的动态极化密度
F F Summa1,2, J H Andersen1, P Lazzeretti2
1DTU Chemistry, Technical University of Denmark, Kemitorvet Bldg. 207, DK-2800 Kongens Lyngby, Denmark.
Journal of chemical theory and computation
|October 5, 2023
概括
电子相关性显著影响电偶极极化密度,揭示了分子计算中的隐藏偏差. 结合集群单双 (CCSD) 方法提供了比简单理论更准确的图像.
科学领域:
- 量子化学 是一个量子化学.
- 计算化学计算化学
- 分子特性 分子特性
背景情况:
- 原点独立的动态电偶极极化密度计算以前仅限于无关联和密度函数理论 (DFT) 方法.
- 了解电子相关性在极化性中的作用对于准确的分子建模至关重要.
研究的目的:
- 在合集群单双 (CCSD) 层面开发和实施原点独立的动态电偶极极极化密度计算.
- 为了研究电子相关性对极化密度分布的影响.
主要方法:
- 在CCSD理论层面上实现原点独立的动态电偶极极化密度.
- 使用哈特里-福克 (HF),CCSD和B3LYP方法对各种分子的极化密度进行点向分析.
主要成果:
- 对极化密度的电子相关效应大大大大大于集成极化值所表明的.
- 显著的偏差,特别是在核间区域,在集成过程中被错误补偿所掩盖.
- 与CCSD和B3LYP之间的比较显示了与CCSD和HF相比偏差的信号反转,突出了电子相关处理的差异.
结论:
- CCSD水平计算显示,电子相关性在塑造动态电偶极极化密度方面发挥着至关重要的作用.
- 标准集成方法可以掩盖极化密度的重要局部偏差,需要点向分析.
- 理论方法的选择 (例如,HF,DFT,CCSD) 显著影响计算的极化密度,电子相关效应的显著差异.
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