Chemical Reactivity

Volume 1: Theories and Principles

1st Edition - May 15, 2023
Editors: Savaş Kaya, Laszlo von Szentpaly, Goncagul Serdaroglu, Lei Guo
Language: English
Paperback ISBN:
9 7 8 - 0 - 3 2 3 - 9 0 2 5 7 - 1
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 9 0 6 1 2 - 8

The growth of technology for chemical assessment has led to great developments in the investigation of chemical reactivity in recent years, but key information is often dispersed… Read more

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The growth of technology for chemical assessment has led to great developments in the investigation of chemical reactivity in recent years, but key information is often dispersed across many different research fields. Combining both original principles and the cutting-edge theories used in chemical reactivity analysis, Chemical Reactivity, Volume 1 present the latest developments in theoretical chemistry and its application for the assessment of chemical processes.

Beginning with an exploration of different theories and principles relating to electronic structure and reactivity of confined electronic systems, the book goes on to highlight key information on such topics as Dyson orbitals, target-ion overlaps, reaction fragility, magnetizability principles and the Fuki function. Density Functional Theory is discussed in relation to numerous different principles and approaches, with further information on constrained methods and diabatic models, bonding evolution theory, orbital-based population analysis models and charge transfer models, and Quantum chemistry and QTAIM.

Consolidating the knowledge of a global team of experts in the field, Chemical Reactivity, Volume 1: Theories and Principles is a useful resource for both students and researchers interested in gaining greater understanding of the principles and theories underpinning chemical reactivity analysis.

Cover image
Title page
Table of Contents
Copyright
Contributors
Introduction to Chemical Reactivity
References
Chapter 1: The importance of correlation in the molecular orbital picture
Abstract
Acknowledgements
1.1. Introduction
1.2. The one-electron picture
1.3. Definitions and concepts
1.4. Canonical Hartree–Fock or Dyson orbitals?
1.5. Final thoughts and conclusion
Note
References
Chapter 2: Dyson orbitals and chemical bonding
Abstract
Acknowledgements
2.1. Introduction
2.2. Theory
2.3. Applications
2.4. Conclusions
References
Chapter 3: Coupled-cluster theory and chemical reactivity
Abstract
3.1. Coupled-cluster methods
3.2. Orbital-optimized methods
3.3. The extended Koopmans' theorem and chemical reactivity
3.4. Ionization potentials
3.5. Electron affinities
3.6. Chemical reactivity
References
Chapter 4: New developments in the Interacting Quantum Atoms (IQA) approach
Abstract
Acknowledgements
4.1. Summary
4.2. Energetic decomposition analysis in chemistry
4.3. The Interacting Quantum Atoms (IQA) approach
4.4. Supported reduced density matrices in IQA
4.5. Chemical insights from the IQA description
4.6. Reactivity under the magnifying glass of IQA
References
Chapter 5: Conceptual Ruedenberg theory of chemical bonds: the necessary step beyond conceptual DFT
Abstract
Acknowledgements
5.1. Introduction to Ruedenberg's bond theory
5.2. Conceptual Ruedenberg theory and conceptual DFT
5.3. Universal potential energy curve based on CRT
5.4. Summary and outlook
Appendix 5.A. Alphabetic glossary of abbreviations and symbols
References
Chapter 6: Electron-density-based analysis and electron density functional theory (DFT) methods
Abstract
Acknowledgement
6.1. Introduction
6.2. Density-based analysis
6.3. Density functional theory (DFT) and TD-DFT method
6.4. Applications
6.5. Conclusions
References
Chapter 7: Information-theoretic concepts in theory of electronic structure and chemical reactivity
Abstract
7.1. Introduction
7.2. Orbital information networks
7.3. Local communications in bond system and electron correlation
7.4. Multisite communications
7.5. Communications in interacting subsystems
7.6. External propagations in reaction complexes
7.7. Probability and current/velocity distributions
7.8. Continuity of wavefunction components
7.9. Probability acceleration, current source, and resultant information
7.10. Entangled and disentangled states of reactants
7.11. Information descriptors of chemical reactivity
7.12. Use of virial theorem partitioning
7.13. Conclusion
References
Chapter 8: Excited-state density functional theory
Abstract
Acknowledgements
8.1. Introduction
8.2. Excited-state theory of Coulomb systems
8.3. Virial theorem
8.4. Coordinate scaling
8.5. Hierarchy of equations for the exchange-correlation and the exchange energies
8.6. Discussion
References
Chapter 9: Reaction fragility method: monitoring evolution of atoms and bonds on a reaction path
Abstract
Acknowledgements
9.1. Introduction: the search for atoms
9.2. Exposing the electron energy by the force constants analysis
9.3. The electron density gradient in the DF connectivity matrix formalism
9.4. The energy expansion in E[N;ν(r)] and E[N;{R}] representations
9.5. Application to a chemical reaction
9.6. Example: the internal proton transfer in formamide
9.7. Discussion: quantitative monitoring of a chemical reaction
9.8. Conclusions and perspectives
Appendix 9.A. Auxiliary notation and proofs for the relations appearing in the text
References
Chapter 10: Looking behind the scenes of Grubbs catalysis with the Unified Reaction Valley Approach
Abstract
10.1. Introduction
10.2. Methodology
10.3. Computational details
10.4. Results and discussion
Appendix 10.A. BSO as function of local mode force constant
References
Chapter 11: The diabatic model of intermediate stabilization for reaction mechanism analysis: a link to valence bond and Marcus theories
Abstract
Acknowledgements
11.1. Introduction
11.2. Diabatic model of intermediate stabilization (DMIS): a three-parabola model
11.3. DMIS for reaction mechanism analysis: changing the focus from transition states to intermediates
11.4. The DMIS perspective on hidden intermediates
11.5. Hammond and Thornton effects: a natural link between DMIS and More O'Ferrall–Jencks diagrams
11.6. Understanding DMIS within a valence bond framework
11.7. The close relationship between DMIS and Marcus theory: changing the paradigm of concerted vs stepwise mechanisms
11.8. Summary and perspective
References
Chapter 12: Main concepts and applications of DFTB approach
Abstract
12.1. Introduction of DFTB
12.2. DFTB method: main concepts and theories
12.3. Applications
12.4. Conclusions
References
Chapter 13: Chemical reactivity insights from the use of constrained methods
Abstract
Acknowledgements
13.1. Introduction
13.2. The constrained minimization procedure
13.3. Results and discussion
13.4. Conclusions
References
Chapter 14: On the analysis of the Fukui function
Abstract
Acknowledgements
14.1. Fukui function
14.2. Topological analysis of the Fukui function
14.3. Some examples
14.4. Last remarks
References
Chapter 15: Analytic calculation of Fukui functions and related reactivity descriptors
Abstract
Acknowledgements
15.1. Introduction
15.2. Formulation
15.3. Computational details
15.4. Results and discussion
15.5. Conclusions
References
Chapter 16: New insights from a bonding evolution theory based on the topological analysis of the electron localization function
Abstract
Acknowledgements
16.1. Introduction
16.2. General remarks concerning the BET formalism
16.3. The case of [4+2] and [2+2] pericyclic cycloadditions
16.4. Conclusions
References
Chapter 17: Experimental quantum chemistry and chemical reactivity
Abstract
Acknowledgements
17.1. Introduction
17.2. Introduction to experimental quantum chemistry
17.3. The terms of the EQC energy partitioning
17.4. EQC in extended systems
17.5. Use of the average electron energy, χ‾, and its connection to electronegativity
17.6. The average electron energy in three dimensions
17.7. EQC and chemical transformations
17.8. Changes to electronegativity with compression
17.9. Q – a descriptor of chemical and physical transformations
17.10. Summary and conclusions
References
Chapter 18: Quantum similarity description of a unique classical and quantum QSPR algorithm in molecular spaces: the connection with Boolean hypercubes, algorithmic intelligence, and Gödel's incompleteness theorems
Abstract
18.1. Introduction
18.2. Chemical, molecular, target, and parameter spaces
18.3. Quantum and classical molecular polyhedra
18.4. Statistical-like vectors associated to a molecular polyhedron
18.5. The main features of a general QSPR theory in molecular space
18.6. Concatenation and decatenation of Boolean hypercubes
18.7. QSPR procedures, Gödel incompleteness theorems, and the dimensionality paradox
18.8. Conclusions
Compliance with ethical standards
References
Index

Savaş Kaya

Savaş Kaya is associate professor at Sivas Cumhuriyet University, Turkey. His research interests lie in theoretical chemistry, computational chemistry, materials science, corrosion science, physical inorganic chemistry, and coordination chemistry.

Affiliations and expertise

Associate Professor, Sivas Cumhuriyet University, Turkey.

Laszlo von Szentpaly

László von Szentpâly currently works at the Faculty of Chemistry, Universität Stuttgart. A member of American Chemical Society with a good reputation in the field of theoretical chemistry, László’s achievements include research on the valence states interaction model of chemical bonding (VSI model) and molecular modelling of ultimate intercalated carcinogens. He has more than 35 research articles, reviews and book chapters on concepts and applications in Density Functional Theory to his name.

Affiliations and expertise

Professor, Institute of Theoretical Chemistry, University of Stuttgart, Germany

Goncagul Serdaroglu

Goncagül Serdaroğlu obtained her PhD degree from Sivas Cumhuriyet University’s Physical chemistry (Theoretical Chemistry) department and was a post-doctoral fellow with Prof. Joseph Vincent Ortiz (Auburn University, USA). At present, she works at Sivas Cumhuriyet University (Math. and Sci. Edu. Department) as Assistant Professor. Her primary research investigates the chemical reactivity behavior of pharmaceutically important molecules using computational tools. Recently, she has focused on the spectroscopic (IR, NMR, UV) and NLO (nonlinear optic) properties of molecular systems. She has published 30 research papers in key computational theoretical chemistry-related journals

Affiliations and expertise

Associate Professor, Faculty of Education, Math. and Sci. Edu., Sivas Cumhuriyet University, Turkey

Lei Guo

Lei Guo received his PhD degree in materials chemistry from the Chongqing university of china. His research is dedicated to synthesis and characterization of organic molecules and their application towards corrosion inhibition property for the protection of metals and alloys from acid corrosion. His interests also encompass theoretical and experimental research in condensed matter physics

Affiliations and expertise

Professor, Tongren University, Tongren, China