He Xin, Lu Tian, Rong Chunying, Liu Shubin, Ayers Paul W, Liu Wenjian
Qingdao Institute for Theoretical and Computational Sciences, Institute of Frontier and Interdisciplinary Science, Shandong University, Qingdao, Shandong 266237, China.
Beijing Kein Research Center for Natural Sciences, Beijing 100022, China.
J Chem Phys. 2023 Aug 7;159(5). doi: 10.1063/5.0159941.
We have witnessed considerable research interest in the recent literature about the development and applications of quantities from the information-theoretic approach (ITA) in density functional theory. These ITA quantities are explicit density functionals, whose local distributions in real space are continuous and well-behaved. In this work, we further develop ITA by systematically analyzing the topological behavior of its four representative quantities, Shannon entropy, two forms of Fisher information, and relative Shannon entropy (also called information gain or Kullback-Leibler divergence). Our results from their topological analyses for 103 molecular systems provide new insights into bonding interactions and physiochemical properties, such as electrophilicity, nucleophilicity, acidity, and aromaticity. We also compare our results with those from the electron density, electron localization function, localized orbital locator, and Laplacian functions. Our results offer a new methodological approach and practical tool for applications that are especially promising for elucidating chemical bonding and reactivity propensity.
我们已经目睹了近期文献中对信息论方法（ITA）在密度泛函理论中的量的发展和应用的大量研究兴趣。这些ITA量是显式密度泛函，其在实空间中的局部分布是连续且行为良好的。在这项工作中，我们通过系统地分析其四个代表性量（香农熵、两种形式的费舍尔信息以及相对香农熵，也称为信息增益或库尔贝克 - 莱布勒散度）的拓扑行为，进一步发展了ITA。我们对103个分子系统进行拓扑分析的结果为键合相互作用和物理化学性质（如亲电性、亲核性、酸度和芳香性）提供了新的见解。我们还将我们的结果与电子密度、电子定位函数、定域轨道定位器和拉普拉斯函数的结果进行了比较。我们的结果为应用提供了一种新的方法学途径和实用工具，这对于阐明化学键合和反应倾向特别有前景。
