Chemical Reactivity in Quantum Mechanics and Information Theory

1 Equalization Principles in Open Subsystems1.1 Introduction1.2 Hypothetical Stages of Electronegativity Equalization1.3 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 Concept1.8 Conclusion

2 Dual Origins of Information Content and State Continuity

2.1 Introduction2.2 Origins of Information Content in Electronic States 2.3 Information Reactivity Criteria2.4 Gaining Information by Eliminating Uncertainties2.5 Continuity Relations 2.6 Component Dynamics in Equilibrium States2.7 Equilibrium Phases and Thermodynamic Entropy2.8 Probability Acceleration and Current Sources2.9 Conclusion

3 Electronic Communications and Chemical Bonds

3.1 Introduction3.2 Orbital Information Networks3.3 Local Communications and Electron Correlation 3.4 Multi-Site Communications 3.5 Communications in Interacting Subsystems3.6 External Propagations in Reaction Complexes3.7 Conclusion

4 Virial Theorem Implications for Displacements in Resultant Gradient Information

4.1 Introduction4.2 Probability and Convection Sources of Structure Information4.3 Resultant Information and Electronic Kinetic Energy4.4 Principle of Thermodynamic Equilibrium in Grand-Ensemble4.5 Information Descriptors of Chemical Reactivity4.6 Virial Theorem Partitioning4.7 Conclusion

5 Simple Models of Charge-Transfer Reactivity

5.1 Introduction5.2 Two-State Description of CT Systems 5.3 Opaque Division Wall5.4 Double-Well Model5.5 Conclusion

6 Entropy and Information Sources

6.1 Introduction6.2 Relations between Densities of Entropy/Information Measures6.3 Affinities, Fluxes, Information Production and Equilibrium 6.4 Quantum Dynamics of Resultant Information6.5 Discussion6.6 Conclusion

7 Equidensity Orbital Description

7.1 Introduction 7.2 Thermodynamic Equidensity Orbitals7.3 Equilibrium Orbitals7.4 Optimum Information Phase7.5 Alternative Representations 7.6 Local-Momentum Concept7.7 Communication Channels7.8 Conclusion

8 Electronic Diffusion and Subsystem Entanglement

8.1 Introduction8.2 Diffusion Analogies8.3 Density Operators of Entangled Subsystems8.4 Kohn-Sham Description of Molecular Fragments8.5 External Correlation Energy8.6 Internal and Overall Correlation Energies8.7 Reaction Stages Revisited8.8 Equilibrium Dissociation Products8.9 Conclusion

9 Nonadditive Entropic Criteria

9.1 Introduction9.2 Entropy-Deficiency Descriptors of Molecular States9.3 Additivity Components in Density Partition Problem9.4 Nonadditive Entropies as Division Criteria9.5 Information Displacements in Molecules9.6 Use of Nonadditive Fisher Information in Bond Localization9.7 Conclusion

10 Miscellanea on Reactive Systems

10.1 Introduction10.2 Charge Sensitivities of Reactants10.3 Alternative Representations and Principal Kernels 10.4 In Situ CT Descriptors of Donor-Acceptor Systems10.5 Implications of Equilibrium and Stability Criteria10.6 Perturbation-Response Relations in Geometric Representations10.7 Descriptors of Electronic-Geometric Interaction 10.8 Compliance Constants and Minimum-Energy Coordinates10.9 Use of Compliance Reactivity Indices10.10 Conclusion

Appendix A: Elements of Information/Communication Theory

A.1 IntroductionA.2 Complementary Classical Measures of Entropy/Information ContentA.3 Entropy Deficiency and Information DistanceA.4 Dependent EventsA.5 Communication SystemsA.6 Variational PrinciplesA.7 Example from Molecular Quantum MechanicsA.8 Conclusion

Appendix B: HSAB Principle and WKB Phase Modeling

B.1 IntroductionB.2 Phase-Modeling and Quasi-Classical ApproximationB.3 Logarithmic Continuity of Subsystem StatesB.4 HSAB PrincipleB.5 Regional HSAB versus Complementary ComplexesB.6 Exploring Phases in Reactive Complexes B.7 Illustrative ExampleB.8 Conclusion

Appendix C: Finite-Difference Electronegativity and Hardness Measures

C.1 IntroductionC.2 Finite Difference Estimates for Molecular SystemsC.3 Description of Acid-Base ComplexesC.4 Conclusion

Appendix D: Equidensity Orbitals for Overlap Distributions

D.1 IntroductionD.2 Orbital Currents and Chemical Bonding D.3 Equidensity Orbitals Conserving Overlap DistributionD.4 Conclusion

Appendix E: Correlated Communication Channels

E.1 Local Hartree-Fock ChannelE.2 Configuration-Interaction NetworksE.3 Correlated Local SystemE.4 Conclusion

Appendix F: Unbiased and Biased Descriptions of Charge Transfer

F.1 IntroductionF.2 Unbiased ApproachF.3 Biased TreatmentF.4 Conclusion