Chemical Reactivity in Quantum Mechanics and Information Theory

Chemical Reactivity in Quantum Mechanics and Information Theory

1st Edition - June 1, 2022

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  • Author: Roman F Nalewajski
  • Paperback ISBN: 9780323956222

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Chemical Reactivity in Quantum Mechanics and Information Theory introduces a thermodynamic-like description of molecular systems and provides an objective treatment of their fragments. The book formulates adequate entropic tools for probing in chemical terms and the electronic structure of molecules and rationalizing reactivity principles. It covers the information origins of chemical bonds, covalent/ionic composition, trends in molecular stability and reactivity, equilibrium polarizations and charge-transfer reconstructions of reactive complexes, as well as the phase/current promotions of molecular substrates. In addition, the book introduces a precise descriptor of molecular fragments and clarifies mostly intuitive semantics of several chemical concepts. Readers will find a precise and unbiased description of chemical reactivity phenomena in Donor-Acceptor systems in terms of quantum states and generalized concepts of Information/Communication theories.

Key Features

  • Generates a new basis for understanding the rules governing molecular processes, information origins of chemical bonding, and its covalent/ionic composition
  • Provides an objective approach to classical issues in modern reactivity theory
  • Offers a unifying information-theoretic perspective on electronic states


Researchers and graduate or advanced undergraduate students in chemistry, physics and molecular biology, interested in new ways of approaching molecular systems, their patterns of chemical bonds, reactivity preferences, and classical issues in chemical theories. Postgraduates and researchers in chemistry and applied physics, in both academic and industrial institutions

Table of Contents

  • 1 Equalization Principles in Open Subsystems
    1.1 Introduction
    1.2 Hypothetical Stages of Electronegativity Equalization
    1.3 Reservoir Interpretation of Equilibria in Open Subsystems
    1.4 Probability and Phase/Current Distributions
    1.5 Latent Flows in Stationary Equilibrium
    1.6 Phase Equalization
    1.7 Local Energy Concept
    1.8 Conclusion

    2 Dual Origins of Information Content and State Continuity
    2.1 Introduction
    2.2 Origins of Information Content in Electronic States
    2.3 Information Reactivity Criteria
    2.4 Gaining Information by Eliminating Uncertainties
    2.5 Continuity Relations
    2.6 Component Dynamics in Equilibrium States
    2.7 Equilibrium Phases and Thermodynamic Entropy
    2.8 Probability Acceleration and Current Sources
    2.9 Conclusion

    3 Electronic Communications and Chemical Bonds
    3.1 Introduction
    3.2 Orbital Information Networks
    3.3 Local Communications and Electron Correlation
    3.4 Multi-Site Communications
    3.5 Communications in Interacting Subsystems
    3.6 External Propagations in Reaction Complexes
    3.7 Conclusion

    4 Virial Theorem Implications for Displacements in Resultant Gradient Information
    4.1 Introduction
    4.2 Probability and Convection Sources of Structure Information
    4.3 Resultant Information and Electronic Kinetic Energy
    4.4 Principle of Thermodynamic Equilibrium in Grand-Ensemble
    4.5 Information Descriptors of Chemical Reactivity
    4.6 Virial Theorem Partitioning
    4.7 Conclusion

    5 Simple Models of Charge-Transfer Reactivity
    5.1 Introduction
    5.2 Two-State Description of CT Systems
    5.3 Opaque Division Wall
    5.4 Double-Well Model
    5.5 Conclusion

    6 Entropy and Information Sources
    6.1 Introduction
    6.2 Relations between Densities of Entropy/Information Measures
    6.3 Affinities, Fluxes, Information Production and Equilibrium
    6.4 Quantum Dynamics of Resultant Information
    6.5 Discussion
    6.6 Conclusion

    7 Equidensity Orbital Description
    7.1 Introduction
    7.2 Thermodynamic Equidensity Orbitals
    7.3 Equilibrium Orbitals
    7.4 Optimum Information Phase
    7.5 Alternative Representations
    7.6 Local-Momentum Concept
    7.7 Communication Channels
    7.8 Conclusion

    8 Electronic Diffusion and Subsystem Entanglement
    8.1 Introduction
    8.2 Diffusion Analogies
    8.3 Density Operators of Entangled Subsystems
    8.4 Kohn-Sham Description of Molecular Fragments
    8.5 External Correlation Energy
    8.6 Internal and Overall Correlation Energies
    8.7 Reaction Stages Revisited
    8.8 Equilibrium Dissociation Products
    8.9 Conclusion

    9 Nonadditive Entropic Criteria
    9.1 Introduction
    9.2 Entropy-Deficiency Descriptors of Molecular States
    9.3 Additivity Components in Density Partition Problem
    9.4 Nonadditive Entropies as Division Criteria
    9.5 Information Displacements in Molecules
    9.6 Use of Nonadditive Fisher Information in Bond Localization
    9.7 Conclusion

    10 Miscellanea on Reactive Systems
    10.1 Introduction
    10.2 Charge Sensitivities of Reactants
    10.3 Alternative Representations and Principal Kernels
    10.4 In Situ CT Descriptors of Donor-Acceptor Systems
    10.5 Implications of Equilibrium and Stability Criteria
    10.6 Perturbation-Response Relations in Geometric Representations
    10.7 Descriptors of Electronic-Geometric Interaction
    10.8 Compliance Constants and Minimum-Energy Coordinates
    10.9 Use of Compliance Reactivity Indices
    10.10 Conclusion

    Appendix A: Elements of Information/Communication Theory
    A.1 Introduction
    A.2 Complementary Classical Measures of Entropy/Information Content
    A.3 Entropy Deficiency and Information Distance
    A.4 Dependent Events
    A.5 Communication Systems
    A.6 Variational Principles
    A.7 Example from Molecular Quantum Mechanics
    A.8 Conclusion

    Appendix B: HSAB Principle and WKB Phase Modeling
    B.1 Introduction
    B.2 Phase-Modeling and Quasi-Classical Approximation
    B.3 Logarithmic Continuity of Subsystem States
    B.4 HSAB Principle
    B.5 Regional HSAB versus Complementary Complexes
    B.6 Exploring Phases in Reactive Complexes
    B.7 Illustrative Example
    B.8 Conclusion

    Appendix C: Finite-Difference Electronegativity and Hardness Measures
    C.1 Introduction
    C.2 Finite Difference Estimates for Molecular Systems
    C.3 Description of Acid-Base Complexes
    C.4 Conclusion

    Appendix D: Equidensity Orbitals for Overlap Distributions
    D.1 Introduction
    D.2 Orbital Currents and Chemical Bonding
    D.3 Equidensity Orbitals Conserving Overlap Distribution
    D.4 Conclusion

    Appendix E: Correlated Communication Channels
    E.1 Local Hartree-Fock Channel
    E.2 Configuration-Interaction Networks
    E.3 Correlated Local System
    E.4 Conclusion

    Appendix F: Unbiased and Biased Descriptions of Charge Transfer
    F.1 Introduction
    F.2 Unbiased Approach
    F.3 Biased Treatment
    F.4 Conclusion

Product details

  • No. of pages: 300
  • Language: English
  • Copyright: © Elsevier 2022
  • Published: June 1, 2022
  • Imprint: Elsevier
  • Paperback ISBN: 9780323956222

About the Author

Roman F Nalewajski

Roman F. Nalewajski is now Professor (Emeritus) of theoretical chemistry at Jagiellonian University in Cracow (Poland). His current research concerns mainly conceptual and methodological issues in quantum chemistry, and particularly density-functional theory (DFT) and information theory (IT) with applications to problems of the chemical bond, molecular electronic structure, and reactivity preferences. His recent interests focus on communication theory of the chemical bond, applying IT in chemical interpretations of molecular states and reactivities, and exploring the phase-equilibria in molecules or their fragments. He is the Author of about 250 scientific publications, two academic textbooks on quantum chemistry (in Polish) and five monographs (in English).

Affiliations and Expertise

Professor Emeritus Jagiellonian University, Krakow, Poland

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