Topological analysis of information-theoretic quantities in density functional theory

Area of Science:

• Quantum Chemistry
• Computational Chemistry
• Theoretical Chemistry

Background:

• Information-theoretic approach (ITA) quantities are gaining traction in density functional theory (DFT).
• These quantities, derived from information theory, offer unique perspectives on electronic structure.
• Their application in understanding chemical properties is an active area of research.

Purpose of the Study:

• To further develop the information-theoretic approach (ITA) in density functional theory.
• To systematically analyze the topological behavior of key ITA quantities: Shannon entropy, Fisher information (two forms), and relative Shannon entropy.
• To provide new insights into chemical bonding and physicochemical properties.

Main Methods:

• Topological analysis of four representative ITA quantities.
• Application of the analysis to a dataset of 103 molecular systems.
• Comparison of ITA quantity behavior with electron density, electron localization function, localized orbital locator, and Laplacian functions.

Main Results:

• The topological analyses revealed new insights into bonding interactions across diverse molecular systems.
• Key physicochemical properties, including electrophilicity, nucleophilicity, acidity, and aromaticity, were elucidated.
• The study demonstrated the utility of ITA quantities in characterizing electronic structure and chemical behavior.

Conclusions:

• The information-theoretic approach provides a valuable methodological advancement for electronic structure analysis.
• ITA quantities serve as practical tools for understanding chemical bonding and predicting reactivity propensity.
• This work establishes a foundation for broader applications of ITA in computational chemistry.