Topological analysis of information-theoretic quantities in density functional theory

• Published in: The Journal of chemical physics Vol. 159; no. 5
• Main Authors: He, Xin, Lu, Tian, Rong, Chunying, Liu, Shubin, Ayers, Paul W, Liu, Wenjian
• Format: Journal Article
• Language: English
• Published: United States 07.08.2023
• ISSN: 1089-7690
• 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.