论文标题
非经验紧密结合理论的自洽方程
Self-Consistent Equations for Nonempirical Tight Binding Theory
论文作者
论文摘要
这项工作介绍了一种称为独立原子Ansatz的密度功能理论的新参考状态。此ANSATZ允许以非相互作用的原子局部化轨道来准确表示电子密度。得出了本地化状态的自洽方程。发现总能量功能非常类似于紧密的结合理论。独立的原子ANSATZ促进了原子间电子和电子核相互作用的部分取消，这允许在弱相互作用极限下推导分析性汉密尔顿基质元素。形式主义提供了收费和能量分解分析，无需额外的费用。它还包括消除自我交流和静态相关错误的机制。先前已经报道了简单模型系统的初始数值结果[Mironenko，J。Phys。化学A 127，7836（2023）]。
A new reference state for density functional theory, termed the independent atom ansatz, is introduced in this work. This ansatz allows for the exact representation of electron density in terms of non-interacting, atom-localized orbitals. Self-consistent equations for localized states are derived. Total energy functional is found to closely resemble tight binding theory. The independent atom ansatz facilitates partial cancellation of inter-atomic electron-electron and electron-nuclear interactions, which allows for the derivation of analytical Hamiltonian matrix elements in a weak interaction limit. The formalism provides charge and energy decomposition analyses at no additional cost. It also includes mechanisms to remove self-interaction and static correlation errors. Initial numerical results for simple model systems have been previously reported [Mironenko, J. Phys. Chem. A 127, 7836 (2023)].
