密度泛函理论
Kohn-Sham方程
超复数
原子轨道
一般化
物理
密度矩阵
含时密度泛函理论
轨道自由密度泛函理论
功能理论
量子力学
缩放比例
计算化学
数学
数学分析
化学
电子
量子
四元数
几何学
出处
期刊:Physical review
日期:2021-11-16
卷期号:104 (5)
被引量:11
标识
DOI:10.1103/physreva.104.052809
摘要
This work presents a rigorous theory to unify the two independent theoretical frameworks of Kohn-Sham (KS) density-functional theory (DFT) and reduced-density-matrix-functional theory (RDMFT). The generalization of the KS orbitals to hypercomplex number systems leads to the hypercomplex KS (HCKS) theory, which extends the search space for the electron density in KS-DFT and reformulates the kinetic energy. The HCKS theory provides a general framework, and different dimensions of the HCKS orbitals lead to different HCKS methods, with KS-DFT and RDMFT being two cases corresponding to the smallest and largest dimensions. Furthermore, a series of tests show that HCKS can capture the multireference nature of strong correlation by dynamically varying fractional occupations, while maintaining the same computational scaling as the KS method. With great potential to overcome the fundamental limitations of the KS method, HCKS creates new possibilities for the development and application of DFT.
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