Molecular acidity: An accurate description with information‐theoretic approach in density functional reactivity theory

Cao, Xiaofang; Rong, Chunying; Zhong, Aiguo; Tian, Laijin; Liu, Shubin

doi:10.1002/jcc.25090

Cited by 82 publications

(76 citation statements)

References 70 publications

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“…We previously proposed to use two equivalent descriptors, MEP (molecular electrostatic potential) and NAO (natural atomic orbital), for the purpose . Our more recent studies using ITA quantities indicated that better results could be obtained. In one of our recent studies shown in Figure , five different categories of acidic series were investigated, accurate descriptions to simultaneously simulate all data sets, a total of 95 points, have been accomplished, with the correlation coefficient better than 0.96.…”

Section: Recent Applicationsmentioning

confidence: 99%

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Information‐theoretic approach in density functional theory and its recent applications to chemical problems

Rong

Wang

Zhao

et al. 2019

WIREs Comput Mol Sci

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101

116

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Using simple functionals of the electron density to appreciate and quantify molecular structure and chemical reactivity properties is a recent endeavor in density functional theory (DFT) toward the development of a new chemical reactivity theory. According to the first Hohenberg–Kohn theorem in DFT, the electron density alone should be able to determine any property in the ground state. Exchange and correlation energies are such properties, so are molecular structure and chemical reactivity, and hence they all should accurately be determined by electron density functionals. Quantities such as Shannon entropy, Fisher information, Ghosh–Berkowitz–Parr entropy, information gain, Onicescu information energy, etc., from the information‐theoretic approach are simple electron density functionals, whose analytical forms are exactly known. In this article, we demonstrate their usefulness and validity to quantify regioselectivity, stereoselectivity, and other structure and reactivity properties. We will outline the current understanding of its theoretical framework at first, and then highlight recent applications to chemical problems including isomeric and conformational stability, electrophilicity and nucleophilicity, strong covalent and weak noncovalent interactions, acidity and basicity, aromaticity and antiaromaticity, and numerous other properties. The effort of employing electron density functionals to quantify chemical concepts should open up a new door for us to ultimately develop a chemical reactivity theory using the DFT language. This article is characterized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Electronic Structure Theory > Density Functional Theory Structure and Mechanism > Molecular Structures Molecular and Statistical Mechanics > Molecular Interactions

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Section: Recent Applicationsmentioning

confidence: 99%

“…Comparisons of experimental p K a data of all five series of compounds with the fitted p K a data using five ITA quantities from (a) the acidic atom and (b) the leaving proton. (Reprinted with permission from Reference . Copyright 2017 John Wiley & Sons)…”

Section: Recent Applicationsmentioning

confidence: 99%

Information‐theoretic approach in density functional theory and its recent applications to chemical problems

Rong

Wang

Zhao

et al. 2019

WIREs Comput Mol Sci

Self Cite

101

116

View full text Add to dashboard Cite

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“…However, there are many options to express the relations defined in Equations and explicitly. Following earlier suggestions in the field the linear combination form of information theoretic quantities has been considered, though other cases are also possible which their applicability may be examined elsewhere. Therefore, the working expressions employed in our calculations take the below forms,

P ([], ρ) = \sum_{j} c_{j} Q_{j}

P ([], ρ) = \sum_{j} c_{j} Q_{j} + c_{ne} V_{ne}

where the summations run over information theoretic quantities Q j and c j and c ne are the expansion coefficients to be determined by the least squares fitting procedure.…”

Section: Theoretical and Computational Basicsmentioning

confidence: 99%

“…Onicescu information energy of order n ,

E_{O}^{n}

E_{O}^{n} ([], ρ) = \frac{1}{n - 1} \int {[ρ (r)]}^{n} d boldr ((), n \geq 2)

and Ghosh–Berkowitz–Parr (GBP) entropy, S GBP ,

S_{GBP} ([], ρ) = \int \frac{3}{2} italickρ ((), boldr) ([], c + ln \frac{t (();, r, ρ)}{t_{TF} (();, r, ρ)}) d boldr

where ρ ( r ) is the ground state electron density of an N ‐electron system which satisfies the normalization condition ∫ ρ ( r ) d r = N and ∇ρ ( r ) is the density gradient. In the Onicescu information energy formula, Equation , the options of n = 2and n = 3 are often employed, though other cases are also possible . Moreover, in the relation of GBP entropy, Equation , k is the Boltzmann constant,

c = \frac{5}{3} + ln \frac{4 normalπ c_{k}}{3}

, t ( r ; ρ ) is the kinetic energy density which is related to the total kinetic energy T S via ∫ t ( r ; ρ ) d r = T S , and t TF ( r ; ρ ) is the Thomas–Fermi kinetic energy density given by t TF ( r ; ρ ) = c k [ ρ ( r )] 5/3 with

c_{k} = \frac{3}{10} {(3 {normalπ}^{2})}^{2 / 3}

.…”

Section: Theoretical and Computational Basicsmentioning

confidence: 99%

“…Putting all these perceptions together, as a proposal it can be anticipated that one or many of these quantities together to be able for describing the kinetic energy component of the correlation energy density functional. As a matter of fact, although for these goals there is an avenue within the traditional DFT as a well‐documented approach in the literature which in turn depends on various approximations for exchange‐correlation functionals, as an alternative route differing from the original idea in DFT, the information functional theory (IFT) framework is also of interest …”

Section: Introductionmentioning

confidence: 99%

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Information theoretic approach provides a reliable description for kinetic component of correlation energy density functional

Badooei

2018

Int J of Quantum Chemistry

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In recent years, much efforts have been invested to apply information theory for different physical and chemical problems. In this regard, one can make use of one or many of the information theoretic quantities together within an approach so‐called information functional theory to describe the energetic components and electronic properties of various systems. In the present contribution, several information theoretic quantities such as Fisher information, Shannon entropy, Onicescu information energy, and Ghosh–Berkowitz–Parr entropy based on the two representations of electron density and shape function are utilized for the prediction of kinetic component of the correlation energy density functional as an important quantity in density functional theory. Taking the atoms and isoelectronic series as benchmark sets we find that with more or less different accountabilities of the considered quantities they can be introduced as reliable measures for the kinetic energy functional. Concerning different natures of the information theoretic quantities with variety of scaling properties and physiochemical propensities, it is shown that instead of describing all data using one of such quantities individually, considering all of them concurrently provides a better view on the prediction of the kinetic component of correlation energy density functional. Hopefully, the information theoretic approach can provide an alternative pathway toward the theoretical prediction and rationalization of important quantities in density functional calculations from the perspective of information theory.

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Impacts of External Electric Fields on Aromaticity and Acidity for Benzoic Acid and Derivatives: Directionality, Additivity, and More

Li,

Wan,

et al. 2024

Electron Density

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Molecular acidity: An accurate description with information‐theoretic approach in density functional reactivity theory

Cited by 82 publications

References 70 publications

Information‐theoretic approach in density functional theory and its recent applications to chemical problems

Information‐theoretic approach in density functional theory and its recent applications to chemical problems

Information theoretic approach provides a reliable description for kinetic component of correlation energy density functional

Impacts of External Electric Fields on Aromaticity and Acidity for Benzoic Acid and Derivatives: Directionality, Additivity, and More

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