Directionality and additivity effects of molecular acidity and aromaticity for substituted benzoic acids under external electric fields

Li, Meng; Wan, Xinjie; Rong, Chunying; Zhao, Dongbo; Liu, Shubin

doi:10.1039/d3cp02982d

Cited by 1 publication

(4 citation statements)

References 88 publications

(146 reference statements)

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“…Analyses using ITA quantities yielded strong linear correlations across all derivatives, regardless of the direction of the applied electric field and the type of the substituent, suggesting that these quantities can be used as reliable descriptors to account for changes of physiochemical properties in an external electric field. 55,56 Also, we recently applied the ITA framework to predict the (static) isotropic molecular polarizability for macromolecules and condensed-phase systems under the periodic boundary condition (PBC). 57,58 Quantitative structure/property relationships between molecular polarizabilities and ITA quantities were established.…”

Section: Applications To External Electric Fields and Largementioning

confidence: 99%

“…We recently systematically examined molecular acidity and aromaticity propensity of benzoic acid and substituted benzoic acids in the external electric field along the direction either parallel or perpendicular to the benzene ring. , Our results show that as the number of substituents increases, both acidity and aromaticity of the substituted benzoic acid are enhanced under the impact of an external electric field, regardless the direction of the applied electric field and the type of the substituent. We also unveiled that, while there are unique features applicable to only one of these properties, directionality and additivity are two common characteristics, independent of the direction of the applied electric field and the type of the substituent as well.…”

Section: Recent Advancesmentioning

confidence: 99%

“…We also unveiled that, while there are unique features applicable to only one of these properties, directionality and additivity are two common characteristics, independent of the direction of the applied electric field and the type of the substituent as well. Analyses using ITA quantities yielded strong linear correlations across all derivatives, regardless of the direction of the applied electric field and the type of the substituent, suggesting that these quantities can be used as reliable descriptors to account for changes of physiochemical properties in an external electric field. , …”

Section: Recent Advancesmentioning

confidence: 99%

“…Theory advances include (i) unveiling the relationship among the four density-based frameworks, , (ii) conducting topological analysis for density-based quantities, (iii) employing Pauli energy derivatives to determine interactions, and (iv) extending this theory to treat excited states . We will also overview our recent applications to appreciate acidity and aromaticity propensities in external electric fields , and estimate polarizability for large molecules and condensed-phase matters using these theoretical tools. , Finally, we will offer a few perspectives for the possible future directions of this theory.…”

Section: Introductionmentioning

confidence: 99%

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Some Recent Advances in Density-Based Reactivity Theory

He,

Li,

Rong

et al. 2024

J. Phys. Chem. A

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Establishing a chemical reactivity theory in density functional theory (DFT) language has been our intense research interest in the past two decades, exemplified by the determination of steric effect and stereoselectivity, evaluation of electrophilicity and nucleophilicity, identification of strong and weak interactions, and formulation of cooperativity, frustration, and principle of chirality hierarchy. In this Featured Article, we first overview the four density-based frameworks in DFT to appreciate chemical understanding, including conceptual DFT, use of density associated quantities, information-theoretic approach, and orbital-free DFT, and then present a few recent advances of these frameworks as well as new applications from our studies. To that end, we will introduce the relationship among these frameworks, determining the entire spectrum of interactions with Pauli energy derivatives, performing topological analyses with informationtheoretic quantities, and extending the density-based frameworks to excited states. Applications to examine physiochemical properties in external electric fields and to evaluate polarizability for proteins and crystals are discussed. A few possible directions for future development are followed, with the special emphasis on its merger with machine learning.

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