Delocalization error: The greatest outstanding challenge in density-functional theory

IF 16.8 2区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Wiley Interdisciplinary Reviews: Computational Molecular Science Pub Date : 2022-07-01 DOI:10.1002/wcms.1631

Kyle R. Bryenton, Adebayo A. Adeleke, Stephen G. Dale, Erin R. Johnson

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引用次数: 36

Abstract

Every day, density-functional theory (DFT) is routinely applied to computational modeling of molecules and materials with the expectation of high accuracy. However, in certain situations, popular density-functional approximations (DFAs) have the potential to give substantial quantitative, and even qualitative, errors. The most common class of error is delocalization error, which is an overarching term that also encompasses the one-electron self-interaction error. In our opinion, its resolution remains the greatest outstanding challenge in DFT development. In this paper, we review the history of delocalization error and provide several complimentary conceptual pictures for its interpretation, along with illustrative examples of its various manifestations. Approaches to reduce delocalization error are discussed, as is its interplay with other shortcomings of popular DFAs, including treatment of non-bonded repulsion and neglect of London dispersion.

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离域误差:密度泛函理论中最大的突出挑战

每天，密度泛函理论(DFT)被常规地应用于分子和材料的计算建模，并期望具有高精度。然而，在某些情况下，流行的密度泛函近似(dfa)有可能产生大量的定量甚至定性错误。最常见的一类误差是离域误差，这是一个包罗万象的术语，也包括单电子自相互作用误差。在我们看来，它的解决仍然是DFT发展中最大的突出挑战。在本文中，我们回顾了离域错误的历史，并提供了一些补充的概念图，以解释它，以及它的各种表现形式的说明性例子。讨论了减少离域误差的方法，以及它与流行的dfa的其他缺点的相互作用，包括处理非键排斥和忽略伦敦色散。本文分类如下:

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Wiley Interdisciplinary Reviews: Computational Molecular Science CHEMISTRY, MULTIDISCIPLINARY-MATHEMATICAL & COMPUTATIONAL BIOLOGY

CiteScore

28.90

自引率

1.80%

发文量

审稿时长

6-12 weeks

期刊介绍： Computational molecular sciences harness the power of rigorous chemical and physical theories, employing computer-based modeling, specialized hardware, software development, algorithm design, and database management to explore and illuminate every facet of molecular sciences. These interdisciplinary approaches form a bridge between chemistry, biology, and materials sciences, establishing connections with adjacent application-driven fields in both chemistry and biology. WIREs Computational Molecular Science stands as a platform to comprehensively review and spotlight research from these dynamic and interconnected fields.