Towards an exact correlated orbital theory for electrons
Towards an exact correlated orbital theory for electrons
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DOI：
10.1016/j.cplett.2009.10.053
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发表时间：
2009-12-08
影响因子：
2.8
通讯作者：
Bartlett, Rodney J.
中科院分区：
文献类型：
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作者：
Bartlett, Rodney J.
Hartree-Fock 和密度泛函理论等有效的单粒子理论在形式和计算上的吸引力提出了一个问题：这些方法可以在多大程度上为原子、分子和固体中电子的选定性质提供准确的结果。一些性质可以在有效的单粒子理论中精确描述，例如主电离势和电子亲和势。这一事实可用于建立相关轨道理论 (COT) 的方程，以保证正确的单粒子能谱。它们建立在此处介绍的基于耦合簇的频率无关自能算子的基础上，该算子将该方法与戴森理论区分开来。 COT 还提供了 Kohn-Sham 密度泛函理论 (DFT) 的替代方案，其目标是将电子密度精确地表示为单个行列式，同时较少关注能谱。对于任何二电子项的估计，COT 提供了主要 Ip 和 Ea 准确性的试金石。这个用于近似 COT 方程的特征以数值方式说明。 (C) 2009 Elsevier B.V. 保留所有权利。
The formal and computational attraction of effective one-particle theories like Hartree-Fock and density functional theory raise the question of how far such approaches can be taken to offer exact results for selected properties of electrons in atoms, molecules, and solids. Some properties can be exactly described within an effective one-particle theory, like principal ionization potentials and electron affinities. This fact can be used to develop equations for a correlated orbital theory (COT) that guarantees a correct one-particle energy spectrum. They are built upon a coupled-cluster based frequency independent self-energy operator presented here, which distinguishes the approach from Dyson theory. The COT also offers an alternative to Kohn-Sham density functional theory (DFT), whose objective is to represent the electronic density exactly as a single determinant, while paying less attention to the energy spectrum. For any estimate of two-electron terms COT offers a litmus test of its accuracy for principal Ip's and Ea's. This feature for approximating the COT equations is illustrated numerically. (C) 2009 Elsevier B.V. All rights reserved.