Chemical reactivity. Volume 2, Approaches and applications /

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.

Bibliographic Details
Corporate Author:	ScienceDirect (Online service)
Other Authors:	Kaya, Savas
Format:	eBook
Language:	English
Published:	Amsterdam : Elsevier, 2023.
Subjects:	Reactivity (Chemistry) Réactivité (Chimie) Reactivitat (Química) Electronic books. Llibres electrònics.
Online Access:	Connect to the full text of this electronic book

Table of Contents:

Front Cover
Chemical Reactivity
Copyright
Contents
Contributors
Introduction to Chemical Reactivity
1 Applications of the quantum theory of atoms in molecules in chemical reactivity
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
1.4.1 Exploration of adsorption properties
1.4.2 Chemical bond breaking
1.5 How can I perform a QTAIM analysis from zero?
1.6 Futures and conclusions
References
2 Exploring chemical space with alchemical derivatives
2.1 Introduction
2.2 Theoretical background and methodology
2.2.1 Chemical space and the Taylor expansion in it
2.2.2 First-, second-, and third-order derivatives: theoretical and computational details
2.2.3 The alchemical coupling method vs. the alchemical derivative approach
2.3 Applications
2.3.1 Annihilation of a proton vs. deprotonation energies
2.3.2 Mutating the central atom in AX4 molecules
2.3.3 Transmuting N2
2.3.4 Replacing CC by BN units in 2D and 3D unsaturated systems: transmuting benzene and C60 to azaborines and BN fullerenes
2.3.4.1 Benzene
2.3.4.2 C60
2.3.5 Back to atoms. Leaving the constraint of isoelectronic transmutations
2.3.5.1 From one neutral atom to its neutral neighbors: moving along the diagonal Z=N
2.3.5.2 Toward ionization energies and first and second electron affinities
2.4 Conclusions
References
3 Quantum chemical descriptors as a modeling framework for large biological structures
3.1 Introduction
3.2 Conceptual DFT for biological systems
3.2.1 Applications in fragments
3.2.2 The biological CDFT endeavor
3.3 PRIMoRDiA software: allowing quantum chemical descriptors for macromolecules
3.3.1 Band reactivity descriptors.
3.3.2 Local hardness problem
3.3.3 The PRIMoRDiA usage, availability, and functionalities
3.3.4 Comparisons between programs that calculate quantum chemical descriptors
3.4 Final considerations
Acknowledgments
References
4 Quantum chemical reactivity, mutations, and reality: narrative essay
4.1 Prelude
4.1.1 Overview
4.2 Mutations
4.2.1 Common words
4.2.2 Tautomerism
4.2.3 Tautomeric mutations and reality
4.2.4 Tautomeric hypothesis: [G·C]WC pair
4.3 Tautomeric mechanism in [A·T]WC pair
4.3.1 Computational methodology
4.3.2 Tautomeric model in [A·T]WC: the neutral state
4.3.3 Tautomeric model in [A·T]WC: the anionic state
4.3.4 Intermediate summary
4.4 Monohydrated pair [A·T]WC
4.4.1 Mutation formation: a novel water-assisted mechanism
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
Acknowledgments
References
5 Volume-based thermodynamics approach in the context of solid-state chemical reactivity analysis
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
5.3.1 Conceptual density functional theory
5.3.2 Conceptual Ruedenberg theory
5.4 Chemical hardness
5.5 Dipole polarizability and VBTA
5.6 Which structural rules should be used in chemical reactivity analysis?
5.6.1 Solid-state double-exchange reactions
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.
6 Predicting reactivity with a general-purpose reactivity indicator
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
Acknowledgments
References
7 Components of density functional reactivity theory-based stabilization energy: descriptors for thermodynamic and kinetic r...
7.1 Introduction
7.2 Theoretical background
7.2.1 Fundamentals
7.2.2 DFT-based reactivity descriptors
7.2.2.1 Global reactivity descriptors
7.2.2.2 Local reactivity descriptors
7.2.2.2.1 Fukui functions
7.2.2.2.2 Local softness
7.2.2.2.3 Local hardness
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)...
7.4.1 Understanding the charge transfer limit of a chemical adduct
7.4.2 Solvent effect on DFRT-based stabilization energy
7.4.3 Correlation between equilibrium constant and stabilization energy
7.4.4 Hammett's linear free energy relationship through density functional reactivity theory
7.5 Conclusions
7.6 Future directions
Acknowledgments
References
8 Electronegativity equalization principle: new approaches and models for the study of chemical reactivity
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
8.3.1 Electronegativity equalization method (EEM)
8.3.1.1 Sanderson's formalism
8.3.1.2 Partial equalization of orbital electronegativity (PEOE) formalism.