Quantifications and Applications of Relative Fisher Information in Density Functional Theory.

Abstract

Though density functional theory is widely accepted as one of the most successful developments in theoretical chemistry in the past few decades, the knowledge of how to apply this new electronic structure theory, to help us better understand chemical processes and transformations, is still an unaccomplished task. The information-theoretic approach is emerging as a viable option for that purpose in the recent literature, providing new insights about steric effect, cooperativity, electrophilicity, nucleophilicity, stereoselectivity, homochirality, etc. In this work, based on the result from a recent paper by one of us [ J. Chem. Phys, 2019, 151, 141103], we present two quantifications of the relative Fisher information and discuss their physiochemical properties and possible applications. To that end, their analytical properties have been elucidated. They have also been applied to six categories of systems to illustrate their applicability. A better descriptor to quantify the single bond rotation barrier has been obtained. The relative Fisher information can also simultaneously determine electrophilicity and nucleophilicity, and effectively describe helical structures with different homochiral and heterochiral propensities. As integral parts of the information-theoretic approach, these newly introduced quantities will provide us with more analytical tools toward the long-term goal of crafting a chemical reactivity theory in the density-based language.