title: Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions.
abstract: The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and steric effects are minor but indispensable. Results obtained in this work should shed new light for better understanding of the factors governing the reactivity for this class of reactions and assisting ongoing efforts for the design of new and more efficient catalysts for such kind of transformations.
authors.affiliation: †School of Pharmacy, Hunan University of Chinese Medicine, Changsha, Hunan 410208, China.
authors.forename: Wenjie
authors.initials: W
authors.lastname: Wu
authors.affiliation: ‡Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China.
authors.forename: Zemin
authors.initials: Z
authors.lastname: Wu
authors.affiliation: ‡Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China.|§Department of Chemistry, McMaster University, Hamilton, Ontario Canada, L8S 4M1.
authors.forename: Chunying
authors.initials: C
authors.lastname: Rong
authors.affiliation: ∥Beijing Kein Research Center for Natural Sciences, Beijing 100022, People's Republic of China.
authors.forename: Tian
authors.initials: T
authors.lastname: Lu
authors.affiliation: †School of Pharmacy, Hunan University of Chinese Medicine, Changsha, Hunan 410208, China.
authors.forename: Ying
authors.initials: Y
authors.lastname: Huang
authors.affiliation: ‡Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China.|⊥Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, United States.
authors.forename: Shubin
authors.initials: S
authors.lastname: Liu
mesh_terms: D001554:Benzene / Q000737:chemistry*; D001880:Boranes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D003198:Computer Simulation; D005740:Gases / Q000737:chemistry; D006858:Hydrofluoric Acid / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D007257:Information Theory; D008956:Models, Chemical; D055672:Static Electricity
chemical_list: D001880:Boranes; D005740:Gases; D002244:Carbon; C021274:boron trifluoride; D006859:Hydrogen; D001554:Benzene; D006858:Hydrofluoric Acid