多态密度函数理论的近似函数
1Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-Ku, Kyoto 606-8502, Japan.
Journal of chemical theory and computation
|June 21, 2024
概括
激发状态的新密度函数理论揭示了电子性质的普遍矩阵函数. 这项工作为多态函数提供了第一个近似,对于准确计算电子相互作用至关重要.
科学领域:
- 量子化学 是一个量子化学.
- 计算物理 计算物理
- 材料科学 材料科学 材料科学
背景情况:
- 密度函数理论 (DFT) 传统上侧重于基本状态.
- 在量子化学中,激发状态带来了重要的计算挑战.
- 精确的电子相互作用建模对于理解化学和物理过程至关重要.
研究的目的:
- 为激发电子状态开发一种新而严格的密度函数理论 (DFT).
- 为动力和电子排斥操作员建立矩阵密度的通用函数.
- 提出多态通用函数的第一个近似.
主要方法:
- 将动力运算子和电子排斥运算子投射到最低电子状态的子空间.
- 将托马斯 - 费米 - 迪拉克 - - 韦兹塞克尔模型和同质电子气相对应能量适应为矩阵函数.
- 确保矩阵函数在基础集合转换下正确转换,并恢复单个状态的基态函数.
主要成果:
- 开发的多态通用函数独立于电子状态的数量,并且具有分析性.
- 该近似准确地复制了LiF的电子排斥运算子的矩阵元素,包括代表状态间相互作用的离对角元素.
- 动能函数显示最大的误差,表明需要改进约束.
结论:
- 这项研究通过引入矩阵函数介绍了激发状态的DFT的显著进步.
- 拟议的近似显示了准确计算电子相互作用的前景,甚至是偏斜的哈密尔顿元素.
- 需要进一步开发,特别是动能函数,以提高精度超出局部密度近似值.
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