Information-Theoretic Approach in Density Functional Reactivity Theory

Liu, Shubin

doi:10.3866/pku.whxb201510302

Cited by 104 publications

(105 citation statements)

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“…These two identities are clear pieces of strong evidence that ITA quantities in DFT are closely correlated . Numerically, we have also observed numerous strong linear correlations among ITA quantities for a number of systems …”

Section: Theoretical Frameworkmentioning

confidence: 71%

“…One is through the shape function σ ( r ), related to ρ ( r ) and N through the following relationship:

ρ ((), r) = italicNσ ((), r)

and satisfying with the normalization condition to unit, ∫ σ ( r ) d r = 1. Similar definitions of ITA quantities, Equations , using the shape function can be obtained, and their relationship with the electron density counterpart can be analytically derived . If we know the results in the electron density representation, we should also know them in the shape function representation.…”

Section: Theoretical Frameworkmentioning

confidence: 99%

“…If we know the results in the electron density representation, we should also know them in the shape function representation. The other possible representation is to redefine all above ITA quantities from the viewpoint of atoms in molecules

\int ρ ((), r) d boldr = \sum_{A} \int_{{normalΩ}_{A}} ρ_{A} ((), r) d boldr = \sum_{A} N_{A} = N .

…”

Section: Theoretical Frameworkmentioning

confidence: 99%

See 2 more Smart Citations

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

Rong

Wang

Zhao

et al. 2019

WIREs Comput Mol Sci

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: Theoretical Frameworkmentioning

confidence: 71%

“…One is through the shape function σ ( r ), related to ρ ( r ) and N through the following relationship:

ρ ((), r) = italicNσ ((), r)

Section: Theoretical Frameworkmentioning

confidence: 99%

See 1 more Smart Citation

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

Rong

Wang

Zhao

et al. 2019

WIREs Comput Mol Sci

116

View full text Add to dashboard Cite

show abstract

“…We have also demonstrated the nonclassical (current) origins of the associated resultant-information production. The present analysis and related treatments of reactivity phenomena [23][24][25][26][27][28] complement the previous classical information approaches to reactive systems, e.g., [82][83][84][85][86].…”

Section: Resultsmentioning

confidence: 77%

Equidensity orbitals in resultant-information description of electronic states

Nalewajski

2019

Theor Chem Acc

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The equidensity orbitals (EO) are used in the resultant entropic description of molecular states which combines the probability and current contributions in the overall information content. Continuities of the modulus and phase components of electronic wavefunctions are examined, and the Harriman-Zumbach-Maschke (HZM) construction of Slater determinants yielding the prescribed electron density is explored. The conditional probability interpretation of (complex) HZM wavefunctions is formulated, the entropy/information contributions due to the state phase component are summarized, and a nonclassical origin of quantum dynamics of the resultant gradient information, related to average kinetic energy of electrons, is emphasized. The phase equilibria maximizing the resultant-entropy measures are explored, and "thermodynamic" phase minimizing the overall gradient information is determined. It generates finite orbital currents giving rise to the vanishing resultant flow of electrons in the system as a whole. Potential use of atomic and molecular EO bases in electronic structure calculations and interpretations in chemistry is discussed, and illustrative example of Gaussian probability distribution is examined in some detail.

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“…In this work, we have attempted the QIT description of the bimolecular donor-acceptor reactive system, including all hypothetical processes that accompany the bond-breaking/bondforming processes of chemical reactions. The present (resultant) information analysis of reactivity phenomena complements earlier (classical) DFT-IT approaches, e.g., [115][116][117][118][119][120][121]. It should be emphasized, however, that the present resultant-information analysis has followed the standard thermodynamic approach to open microscopic systems, which does not imply any new "thermodynamic" transcription of DFT, see, e.g., [120,121].…”

Section: Discussionmentioning

confidence: 75%

Role of electronic kinetic energy and resultant gradient information in chemical reactivity

Nalewajski

2019

J Mol Model

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The role of resultant gradient-information concept, reflecting the kinetic energy of electrons, in shaping the molecular electronic structure and reactivity preferences of open reactants is examined. This quantum-information descriptor combines contributions due to both the modulus (probability) and phase (current) components of electronic wavefunctions. The importance of resultant entropy/information concepts for distinguishing the bonded (entangled) and nonbonded (disentangled) states of molecular fragments is emphasized and variational principle for the minimum of ensemble-average electronic energy is interpreted as a physically equivalent rule for the minimum of resultant gradient-information, and the information descriptors of charge-transfer (CT) phenomena are introduced. The in situ reactivity criteria, represented by the populational CT derivatives of the ensembleaverage values of electronic energy or resultant information, are mutually related, giving rise to identical predictions of electron flows in the acid(A)base(B), reactive systems. The virial theorem decomposition of electronic energy is used to reveal changes in the resultant information content due to the chemical bond formation, and to rationalize the Hammond postulate of reactivity theory. The complementarity principle of structural chemistry is confronted with the regional hard (soft) acid and bases (HSAB) rule by examining the polarizational and relaxational flows in such acceptor-donor reactive systems, responses to the external potential and CT displacements, respectively. The frontier-electron basis of the HSAB principle is reexamined and the intra-and inter-reactant communications in A-B systems are explored.

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Information-Theoretic Approach in Density Functional Reactivity Theory

Cited by 104 publications

References 0 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

Equidensity orbitals in resultant-information description of electronic states

Role of electronic kinetic energy and resultant gradient information in chemical reactivity

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