Chemical Reactivity in Confined Systems - Theory, Modelling and Applications

An insightful analysis of confined chemical systems for theoretical and experimental scientists
 
Chemical Reactivity in Confined Systems: Theory and Applications presents a theoretical basis for the molecular phenomena observed in confined spaces. The book highlights state-of-the-art theoretical and computational approaches, with a focus on obtaining physically relevant clarification of the subject to enable the reader to build an appreciation of underlying chemical principles.
 
The book includes real-world examples of confined systems that highlight how the reactivity of atoms and molecules change upon encapsulation. Chapters include discussions on recent developments related to several host-guest systems, including cucurbit[n]uril, ExBox+4, clathrate hydrates, octa acid cavitand, metal organic frameworks (MOFs), covalent organic frameworks (COFs), zeolites, fullerenes, and carbon nanotubes. Readers will learn how to carry out new calculations to understand the physicochemical behavior of confined quantum systems.
 
Topics covered include:
* A thorough introduction to global reactivity descriptors, including electronegativity, hardness, and electrophilicity
* An exploration of the Fukui function, as well as dual descriptors, higher order derivatives, and reactivity through information theory
* A practical discussion of spin dependent reactivity and temperature dependent reactivity
* Concise treatments of population analysis, reaction force, electron localization functions, and the solvent effect on reactivity
 
Perfect for academic researchers and graduate students in theoretical and computational chemistry and confined chemical systems, Chemical Reactivity in Confined Systems: Theory and Applications will also earn a place in the libraries of professionals working in the areas of catalysis, supramolecular chemistry, and porous materials.

List of contents

Preface xiii
 
1 Effect of Confinement on the Translation-Rotation Motion of Molecules: The inelastic neutron scattering selection rule 1
 
1.1 Introduction 1
 
1.2 Diatomics in C60: entanglement, TR coupling, symmetry, basis representation, and energy level structure 4
 
1.2.1 Entanglement Induced Selection Rules 4
 
1.2.2 H@C60 5
 
1.2.3 H2@C60 7
 
1.2.3.1 Symmetry 7
 
1.2.3.2 Spherical basis and eigenstates 7
 
1.2.3.3 Energy level ordering with respect to lambda 8
 
1.2.4 HX@C60 10
 
1.3 INS selection rule for spherical (Kh) symmetry 11
 
1.3.1 Inelastic Neutron Scattering 11
 
1.3.2 Group Theory Derivation of the INS Selection Rule 12
 
1.3.2.1 Group-theory-based INS selection rule for cylindrical (C infinity v) environments 12
 
1.3.2.2 Group-theory-based INS selection rule for spherical (Kh) environments 12
 
1.3.3 Specific Systems, Quantum Numbers, and Basis Sets 13
 
1.3.3.1 H@sphere 14
 
1.3.3.2 H2@sphere 14
 
1.3.3.3 HX@sphere 15
 
1.3.4 Beyond Diatomic Molecules 15
 
1.3.4.1 H2O@sphere 15
 
1.3.4.2 CH4@sphere 17
 
1.3.4.3 Any guest molecule in any spherical (Kh) environment 18
 
1.4 INS selection rules for non-spherical structures 18
 
1.5 Summary and conclusions 20
 
Acknowledgments 22
 
References 22
 
2 Pressure-induced phase transitions 25
 
2.1 Pressure, a property of all flavours, and its importance for the Universe and life 25
 
2.2 Pressure: isotropic and anisotropic, positive and negative 26
 
2.3 Changes of the state of matter 27
 
2.4 Compression of solids 30
 
2.4.1 Isotropic or anisotropic compressibility 30
 
2.4.2 Negative linear compressibility 30
 
2.4.3 Negative area compressibility 31
 
2.4.4 Anomalous compressibility changes at high pressure 31
 
2.5 Structural solid-solid transitions 32
 
2.5.1 Structural phase transitions accompanied by volume collapse 32
 
2.5.2 Effects of volume collapse on free energy 33
 
2.5.3 Structure-influencing factors at compression 34
 
2.5.4 Changes in the nature of chemical bonding upon compression and upon phase transitions 35
 
2.6 Selected classes of magnetic and electronic transitions 36
 
2.6.1 High Spin-Low Spin transitions 36
 
2.6.2 Electronic com- vs disproportionation 37
 
2.6.3 Metal-to-metal charge transfer 37
 
2.6.4 Neutral-to-Ionic transitions 37
 
2.6.5 Metallization of insulators (and resisting it) 38
 
2.6.6 Turning metals into insulators 39
 
2.6.7 Superconductivity of elements and compounds 39
 
2.6.8 Topological phase transitions 41
 
2.7 Modelling and predicting HP phase transitions 41
 
Acknowledgements 42
 
References 42
 
3 Conceptual DFT and Confinement 49
 
3.1 Introduction and Reading Guide 49
 
3.2 Conceptual DFT 50
 
3.3 Confinement and Conceptual DFT 52
 
3.3.1 Atoms: global descriptors 52
 
3.3.2 Molecules: global and local descriptors 56
 
3.3.2.1 Electron Affinities 57
 
3.3.2.2 Hardness and electronic Fukui function 59
 
3.3.2.3 Inclusion of pressure in the E = E [N,v] functional 63
 
3.4 Conclusions 65
 
Acknowledgements 65
 
References 66
 
4 Electronic structure of systems confined by several spatial restrictions 69
 
4.1 Introduction 69
 
4.2 Confinement imposed by impenetrable walls 69
 
4.3 Confinement imposed by soft walls 72
 
4.4 Beyond confinement models 74
&nbs

About the author

Pratim Kumar Chattaraj is an Institute Chair Professor, Department of Chemistry, Indian Institute of Technology Kharagpur, India and a J.C. Bose National Fellow. His research focuses on density functional theory, ab-initio calculations, nonlinear dynamics and aromaticity in metal clusters.
Debdutta Chakraborty is a Research Associate in the Department of Chemistry at Katholieke Universiteit Leuven, Belgium. His research focus is on computational quantum chemistry, direct dynamics simulations, atmospheric chemistry and quantum trajectories.

Summary

An insightful analysis of confined chemical systems for theoretical and experimental scientists

Chemical Reactivity in Confined Systems: Theory and Applications presents a theoretical basis for the molecular phenomena observed in confined spaces. The book highlights state-of-the-art theoretical and computational approaches, with a focus on obtaining physically relevant clarification of the subject to enable the reader to build an appreciation of underlying chemical principles.

The book includes real-world examples of confined systems that highlight how the reactivity of atoms and molecules change upon encapsulation. Chapters include discussions on recent developments related to several host-guest systems, including cucurbit[n]uril, ExBox+4, clathrate hydrates, octa acid cavitand, metal organic frameworks (MOFs), covalent organic frameworks (COFs), zeolites, fullerenes, and carbon nanotubes. Readers will learn how to carry out new calculations to understand the physicochemical behavior of confined quantum systems.

Topics covered include:
* A thorough introduction to global reactivity descriptors, including electronegativity, hardness, and electrophilicity
* An exploration of the Fukui function, as well as dual descriptors, higher order derivatives, and reactivity through information theory
* A practical discussion of spin dependent reactivity and temperature dependent reactivity
* Concise treatments of population analysis, reaction force, electron localization functions, and the solvent effect on reactivity

Perfect for academic researchers and graduate students in theoretical and computational chemistry and confined chemical systems, Chemical Reactivity in Confined Systems: Theory and Applications will also earn a place in the libraries of professionals working in the areas of catalysis, supramolecular chemistry, and porous materials.

Product details

• Authors: Debdutta Chakraborty, Pk Chattaraj, Pratim K. Chakraborty Chattaraj, Pratim Kumar Chattaraj, Pratim Kumar Chakraborty Chattaraj
• Assisted by: Chakraborty (Editor), Chakraborty (Editor), Debdutta Chakraborty (Editor), Pratim K. Chattaraj (Editor), Pratim Kumar Chattaraj (Editor), Chattaraj Pratim Kumar (Editor), Prati Kumar Chattaraj (Editor), Pratim Kumar Chattaraj (Editor)
• Publisher: Wiley, John and Sons Ltd
• Languages: English
• Product format: Hardback
• Released: 30.06.2021
• EAN: 9781119684022
• ISBN: 978-1-119-68402-2
• No. of pages: 448
• Subjects: Natural sciences, medicine, IT, technology > Chemistry > Physical chemistry; Chemie, Katalyse, chemistry, Catalysis, Materialwissenschaften, Materials science, Computational Chemistry u. Molecular Modeling, Computational Chemistry & Molecular Modeling, Poröse Materialien, Porous Materials