Self-Consistent Calculation of the Localized Orbital Scaling Correction for Correct Electron Densities and Energy-Level Alignments in Density Functional Theory,The Journal of Physical Chemistry Letters

当前位置： X-MOL 学术 › J. Phys. Chem. Lett. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Self-Consistent Calculation of the Localized Orbital Scaling Correction for Correct Electron Densities and Energy-Level Alignments in Density Functional Theory
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-11-20 , DOI: 10.1021/acs.jpclett.0c03133
Yuncai Mei , Zehua Chen , Weitao Yang ₁

Affiliation

The recently developed localized orbital scaling correction (LOSC) method shows the ability to systematically and size-consistently reduce the delocalization error existing in conventional density functional approximations (DFAs). However, the application of LOSC to DFAs was mainly through a post self-consistent field (SCF) manner, and few results from applying LOSC to DFAs in an SCF manner have been reported. The reason is that the originally proposed SCF approach to SCF–LOSC calculation uses an approximate Hamiltonian and encounters convergence problems easily in practice. In this work, we develop a new SCF approach with a correct Hamiltonian and achieve reliable SCF–LOSC calculations. We demonstrate the capability of the new SCF approach for SCF–LOSC to correctly describe the electron densities, total energies, and energy-level alignment for the molecular dissociation process, while conventional DFAs or LOSC–DFAs with post-SCF calculations show large errors. This work demonstrates that the new SCF approach for SCF–LOSC would be a promising method for studying problems for correct electron densities and energy-level alignments in large systems.

中文翻译：

密度泛函理论中正确电子密度和能级排列的局域轨道标度校正的自洽计算

最近开发的定域轨道标度校正（LOSC）方法显示出系统地、尺寸一致地减少传统密度函数近似（DFA）中存在的离域误差的能力。然而，LOSC在DFA中的应用主要是通过后自洽场（SCF）方式，而以SCF方式将LOSC应用于DFA的结果很少有报道。原因是最初提出的 SCF-LOSC 计算 SCF 方法使用近似哈密顿量，在实践中很容易遇到收敛问题。在这项工作中，我们开发了一种具有正确哈密顿量的新 SCF 方法，并实现了可靠的 SCF-LOSC 计算。我们证明了 SCF-LOSC 的新 SCF 方法能够正确描述分子解离过程的电子密度、总能量和能级排列，而传统的 DFA 或采用后 SCF 计算的 LOSC-DFA 显示出较大的误差。这项工作表明，SCF-LOSC 的新 SCF 方法将是研究大型系统中正确电子密度和能级对准问题的一种有前景的方法。

更新日期：2020-12-03

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11