Chemical Reactivity

Volume 2: Approaches and Applications

1st Edition - May 15, 2023
Imprint: Elsevier
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 9 - 5
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 9 0 6 2 8 - 9

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. Exploring both traditional and advanced methods, Chemical Reactivity, Volume 2: Approaches and Applications present the latest approaches and strategies for the computational assessment of chemical reactivity.

Following an insightful introduction, the book begins with an overview of conformer searching techniques before progressing to explore numerous different techniques and methods, including confined environments, quantum similarity descriptors, volume-based thermodynamics and polarizability. A unified approach to the rules of aromaticity is followed by methods for assessing interaction energies and the role of electron density for varied different analyses. Algorithms for confirmer searching, partitioning and a whole range of quantum chemical methods are also discussed.

Consolidating the knowledge of a global team of experts in the field, Chemical Reactivity, Volume 2: Approaches and Applications is a useful resource for both students and researchers interested in applying and refining their use of the latest approaches for assessing chemical reactivity in their own work.

Cover image
Title page
Table of Contents
Copyright
Contributors
Introduction to Chemical Reactivity
References
Chapter 1: Applications of the quantum theory of atoms in molecules in chemical reactivity
Abstract
1.1. Introduction
1.2. Fundamentals of the quantum theory of atoms in molecules
1.3. Importance of the Laplacian of electron density and QTAIM applications
1.4. Reactivity and chemical bonding
1.5. How can I perform a QTAIM analysis from zero?
1.6. Futures and conclusions
References
Chapter 2: Exploring chemical space with alchemical derivatives
Abstract
2.1. Introduction
2.2. Theoretical background and methodology
2.3. Applications
2.4. Conclusions
References
Chapter 3: Quantum chemical descriptors as a modeling framework for large biological structures
Abstract
Acknowledgements
3.1. Introduction
3.2. Conceptual DFT for biological systems
3.3. PRIMoRDiA software: allowing quantum chemical descriptors for macromolecules
3.4. Final considerations
References
Chapter 4: Quantum chemical reactivity, mutations, and reality: narrative essay
Abstract
Acknowledgements
4.1. Prelude
4.2. Mutations
4.3. Tautomeric mechanism in [A⋅T]WC pair
4.4. Monohydrated pair [A⋅T]WC
4.5. Computational model of protons transfers in water-preopened A⋅T pair: final remarks
4.6. Conclusions: quo vadis mutations?
4.7. Afterword: thoughts on mound
References
Chapter 5: Volume-based thermodynamics approach in the context of solid-state chemical reactivity analysis
Abstract
5.1. Introduction to VBTA
5.2. Ionic models as precursors of valence state models
5.3. Conceptual density functional theory and conceptual Ruedenberg theory in relation to VBTA
5.4. Chemical hardness
5.5. Dipole polarizability and VBTA
5.6. Which structural rules should be used in chemical reactivity analysis?
5.7. An inverse relation between entropy and magnetizability
5.8. Fukui potential and lattice energy
5.9. VBT approach for the calculation of ambient isobaric heat capacities Cp, surface tension, and compressibility
5.10. Summary
References
Chapter 6: Predicting reactivity with a general-purpose reactivity indicator
Abstract
Acknowledgements
6.1. Introduction
6.2. Perturbative perspective on the chemical reaction prediction problem
6.3. Applications of the perturbative perspective model
6.4. General-purpose reactivity indicator
6.5. GPRI applications
6.6. Conclusions
References
Chapter 7: Components of density functional reactivity theory-based stabilization energy: descriptors for thermodynamic and kinetic reactivity
Abstract
Acknowledgements
7.1. Introduction
7.2. Theoretical background
7.3. Parr and Pearson equation, its modification, and utility
7.4. Modifications and recent applications of DFRT-based comprehensive decomposition analysis of stabilization energy (CDASE) scheme
7.5. Conclusions
7.6. Future directions
References
Chapter 8: Electronegativity equalization principle: new approaches and models for the study of chemical reactivity
Abstract
8.1. A brief introduction to the concept of electronegativity
8.2. Electronegativity equalization principle
8.3. Some approaches and models that have been developed based on the electronegativity equalization principle
References
Chapter 9: Electrophilic aromatic substitution: from isolated reactant approaches to chemical reactivity in solvent
Abstract
Acknowledgements
9.1. Introduction
9.2. Application of reactivity indices from conceptual DFT
9.3. Toward an updated and more complete mechanistic picture of the electrophilic aromatic substitution
9.4. A unifying valence bond perspective on the electrophilic aromatic substitution reaction
9.5. Conclusions
References
Chapter 10: Lessons from the maximum hardness principle
Abstract
Acknowledgements
10.1. Introduction to electronic hardness and related properties: formal considerations
10.2. HSAB rule
10.3. The maximum hardness principle (MHP) and the minimum polarizability principle (MPP)
10.4. Differentiating between MHP and the generalized maximum hardness principle (GMHP)
10.5. Narrowing down the generalized maximum hardness principle (GMHP)
10.6. “Problem” with metallic matter
10.7. Superconductors meet MHP (aka metals return)
10.8. GMHP across the periodic table of chemical elements
10.9. Complex solids: polymorphism, phase separation, and insulators
10.10. Matter at elevated pressure: GMHP still at work!
10.11. Chemical reactions: GMHP as an intuitive guide
10.12. Summary and outlook
References
Chapter 11: Electron density to analyze acids and bases of Lewis: computational tools
Abstract
11.1. Introduction
11.2. Density functional theory
References
Chapter 12: Phase modeling of donor–acceptor systems, continuity relations, and resultant entropy/information descriptors
Abstract
12.1. Introduction
12.2. Phase modeling
12.3. Relation to quasi-classical approximation
12.4. Logarithmic continuity of subsystem states
12.5. Complementary and HSAB coordinations in donor–acceptor systems
12.6. Illustrative example
12.7. Continuity relations and resultant gradient information
12.8. Need for quantum measures of the state entropy/information content
12.9. Conclusion
References
Chapter 13: Understanding odd-electron halogen bonding in the light of chemical reactivity indices
Abstract
Acknowledgements
13.1. Introduction
13.2. Odd-electron σ-bond
13.3. Odd-electron halogen bond
13.4. Concluding remarks and future prospect in this direction
References
Chapter 14: Using conceptual DFT for studies of metal complexes: some interesting examples
Abstract
14.1. Introduction
14.2. Interesting examples of applications of CDFT for various metal compounds/complexes
14.3. Conclusions and perspectives
References
Chapter 15: Noniterative solvation energy method based on atomic charges
Abstract
15.1. Introduction
15.2. The COSMO method
15.3. Correction (nonelectrostatic) term
15.4. Least-squares parameter fitting
15.5. Atomic charges
15.6. Results
15.7. Conclusions and outlook
References
Chapter 16: Chemical reactivity in confined environment
Abstract
Acknowledgements
16.1. Introduction
16.2. Mathematical realization of chemical reactivity parameters
16.3. Chemical reactivity under confined environment
16.4. Confinement in other systems
16.5. Conclusions
References
Chapter 17: Structure prediction using reactivity descriptors
Abstract
Acknowledgements
17.1. Introduction
17.2. Theoretical background
17.3. How to obtain a practical quantification of local reactivity through FF analysis
17.4. Early attempts to use the Fukui function to explore PES
17.5. Hybrid methodologies using Fukui function to explore PES
17.6. Conclusions and perspectives
17.7. Computational details
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

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Chemical Reactivity

Volume 2: Approaches and Applications

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Savaş Kaya

Laszlo von Szentpaly

Goncagul Serdaroglu

Lei Guo

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