Shannon entropy of chemical changes:SN2 displacement reactions

Minhhuy, H; Schmider, Hartmut; Weaver, Donald F.; Smith, Vedene H.; Sagar, Robin P.; Esquivel, Rodolfo O.

doi:10.1002/(sici)1097-461x(2000)77:1<376::aid-qua37>3.0.co;2-3

Cited by 36 publications

(5 citation statements)

References 25 publications

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“…The phase aspect of molecular states was shown to be vital for distinguishing the hypothetical bonded (entangled) and nonbonded (disentangled) states of molecular subsystems in reactive systems, for the same set of the fragment electron densities. The resultant-information analysis of reactivity phenomena complements earlier classical IT approaches to chemical reactions [110][111][112] as well as the catastrophe-theory or quantum-topology descriptions [113][114][115]. One also recalls a close connection between the ELF criterion of electron localization and the nonadditive component of the molecular Fisher information [46,56].…”

Section: Discussionmentioning

confidence: 70%

Understanding Electronic Structure and Chemical Reactivity: Quantum-Information Perspective

Nalewajski

2019

Applied Sciences

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Several applications of quantum mechanics and information theory to chemical reactivity problems are presented with emphasis on equivalence of variational principles for the constrained minima of the system electronic energy and its kinetic energy component, which also determines the overall gradient information. Continuities of molecular probability and current distributions, reflecting the modulus and phase components of molecular wavefunctions, respectively, are summarized. Resultant measures of the entropy/information descriptors of electronic states, combining the classical (probability) and nonclassical (phase/current) contributions, are introduced, and information production in quantum states is shown to be of a nonclassical origin. Importance of resultant information descriptors for distinguishing the bonded (entangled) and nonbonded (disentangled) states of reactants in acid(A)–base(B) systems is stressed and generalized entropy concepts are used to determine the phase equilibria in molecular systems. The grand-canonical principles for the minima of electronic energy and overall gradient information allow one to explore relations between energetic and information criteria of chemical reactivity in open molecules. The populational derivatives of electronic energy and resultant gradient information give identical predictions of electronic flows between reactants. The role of electronic kinetic energy (resultant gradient information) in chemical-bond formation is examined, the virial theorem implications for the Hammond postulate of reactivity theory are explored, and changes of the overall structure information in chemical processes are addressed. The frontier-electron basis of the hard (soft) acids and bases (HSAB) principle is reexamined and covalent/ionic characters of the intra- and inter-reactant communications in donor-acceptor systems are explored. The complementary A–B coordination is compared with its regional HSAB analog, and polarizational/relaxational flows in such reactive systems are explored.

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Section: Discussionmentioning

confidence: 70%

Understanding Electronic Structure and Chemical Reactivity: Quantum-Information Perspective

Nalewajski

2019

Applied Sciences

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“…Using Equation ( 26), the authors of [77] found that the minimum of ΔSKL corresponds to the activation barrier and TS of the studied chemical reactions (proton transfer and SN2 reaction) (Figure 8). As for the application of the continual information entropy approach to chemical reactions, we pay attention to two works [73,76]. The work of Ho et al [76] used S ρ and some related quantities to check their changes upon simplest S N 2 displacement reactions.…”

Section: Moleculementioning

confidence: 99%

“…As for the application of the continual information entropy approach to chemical reactions, we pay attention to two works [73,76]. The work of Ho et al [76] used S ρ and some related quantities to check their changes upon simplest S N 2 displacement reactions. Although function S ρ = f (ξ) (ξ is the reaction coordinate) still shows the redistribution of electron density upon the reactions, the authors have not found any specific behavior of the function in the stationary points lying on the reaction path (minima of reactants/products and saddle point of a transition state).…”

Section: Moleculementioning

confidence: 99%

Information Entropy in Chemistry: An Overview

Sabirov

Shepelevich

2021

Entropy

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Basic applications of the information entropy concept to chemical objects are reviewed. These applications deal with quantifying chemical and electronic structures of molecules, signal processing, structural studies on crystals, and molecular ensembles. Recent advances in the mentioned areas make information entropy a central concept in interdisciplinary studies on digitalizing chemical reactions, chemico-information synthesis, crystal engineering, as well as digitally rethinking basic notions of structural chemistry in terms of informatics.

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“…Moreover, Balakrishnan et al showed that information-theoretic entropies increase to a maximum in a dynamical study when studying the time evolution of a bimolecular exchange reaction. Within the context of Information Theory, Shannon entropy studies revealed geometrical aspects of the density that are not present in the energy profile of elementary S N 2 reactions . Moreover, Knoerr et al found correlations between charge density aspects of the S N 2 reaction and the energy-related measures of Shaik et al Later, Tachibana identified the chemical bond-forming of model reactions through the kinetic energy density to identify several stages of the reactions along the IRC.…”

Section: Introductionmentioning

confidence: 99%

“…Within the context of Information Theory, Shannon entropy studies revealed geometrical aspects of the density that are not present in the energy profile of elementary S N 2 reactions. 23 Moreover, Knoerr et al 24 found correlations between charge density aspects of the S N 2 reaction and the energy-related measures of Shaik et al 25 Later, Tachibana 26 identified the chemical bond-forming of model reactions through the kinetic energy density to identify several stages of the reactions along the IRC. Also, long-range dipole moments have been useful for ion–molecule reactions to control their reaction path with laser fields.…”

Section: Introductionmentioning

confidence: 99%

3DInformation-Theoretic Analysis of the Simplest Hydrogen Abstraction Reaction

2023

Self Cite

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We investigate the course of an elementary chemical reaction from the perspective of information theory in 3D space through the hypersurface of several information-theoretic (IT) functionals such as disequilibrium (D), Shannon entropy (S), Fisher information (I), and the complexity measures of Fisher–Shannon (FS) and López–Mancini–Calbet (LMC). The probe for the study is the hydrogenic identity abstraction reaction. In order to perform the analysis, the reactivity pattern of the reaction is examined by use of the aforementioned functionals of the single-particle density, which is analyzed in position (r) and momentum (p) spaces. The 3D analyses revealed interesting reactivity patterns in the neighborhood of the intrinsic reaction coordinate (IRC) path, which allow to interpret the reaction mechanism for this reaction in a novel manner. In addition, the chemically interesting regions that have been characterized through the information functionals and their complexity measures are depicted and analyzed in the framework of the three-dimensional structure of the information-theoretical data of a chemical reaction, that is, the reactant/product (R/P) complexes, the transition state (TS), and the ones that are only revealed through IT measures such as the bond-cleavage energy region (BCER), the bond-breaking/forming (B-B/F) region, and the spin-coupling (SC) process. Furthermore, focus has been placed on the diagonal part of the hypersurface of the IT functionals, aside from the IRC path itself, with the purpose of analyzing the dissociation process of the triatomic transition-state complex that has revealed other interesting features of the bond-breaking (B-B) process. In other respects, it is shown throughout the combined analyses of the 3D structure of the IT functionals in conjugated spaces that the chemically significant regions occurring at the onset of the TS are completely characterized by information-theoretic aspects of localizability (S), uniformity (D), and disorder. Further, novel regions of low complexity seem to indicate new boundaries for chemically stable complex molecules. Finally, the study reveals that the chemical reaction occurs at low-complexity regions, where the concurrent phenomena take place: bond-breaking/forming (B-B/F), bond-cleavage energy reservoirs (BCER), spin-coupling (SC), and transition state (TS).

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Shannon entropy of chemical changes:SN2 displacement reactions

Cited by 36 publications

References 25 publications

Understanding Electronic Structure and Chemical Reactivity: Quantum-Information Perspective

Understanding Electronic Structure and Chemical Reactivity: Quantum-Information Perspective

Information Entropy in Chemistry: An Overview

3DInformation-Theoretic Analysis of the Simplest Hydrogen Abstraction Reaction

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