Chemical reactivity in confined systems : theory, modelling and applications /: theory, modelling and applications. (2021)

• Record Type: Book
• Further Information: Note: Edited by Pratim Kumar Chattaraj, Debdutta Chakraborty.
• Editors: Chattaraj, Pratim Kumar; Chakraborty, Debdutta
• 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 '� 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 ∞ '� ) 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 H2 O@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 4.5 Conclusions 77 References 77 5 Unveiling the Mysterious Mechanisms of Chemical Reactions 81 5.1 Introduction 81 5.1.1 Context 81 5.1.2 Ideas and methods 82 5.1.3 Application 82 5.2 Energy and reaction force 83 5.2.1 The reaction force analysis (RFA) 83 5.2.2 RFA-based energy decomposition 84 5.2.3 Marcus potential energy function 85 5.2.4 Marcus RFA 86 5.3 Electronic activity along a reaction coordinate 87 5.3.1 Chemical potential, hardness, and electrophilicity index 87 5.3.2 The reaction electronic flux (REF) 88 5.3.2.1 Physical decomposition of REF 88 5.3.2.2 Chemical decomposition of REF 89 5.4 An application: the formation of aminoacetonitrile 90 5.4.1 Energetic analysis 91 5.4.2 Reaction mechanisms 91 5.5 Conclusions 94 Acknowledgments 95 References 95 6 A Perspective on the So-called Dual Descriptor 99 6.1 Introduction: conceptual DFT 99 6.2 The Dual Descriptor: fundamental aspects 99 6.2.1 Initial formulation 99 6.2.2 Alternative formulations 100 6.2.2.1 Derivative formulations 100 6.2.2.2 Link with Frontier Molecular Orbital theory 101 6.2.2.3 State-specific development 101 6.2.2.4 MO degeneracy 102 6.2.2.5 Quasi degeneracy 102 6.2.2.6 Spin polarization 103 6.2.2.7 Grand canonical ensemble derivation 105 6.2.3 Real-space partitioning 105 6.2.4 Dual descriptor and chemical principles 106 6.2.4.1 Principle of Maximum Hardness 106 6.2.4.2 Local hardness descriptors 106 6.2.4.3 Local electrophilicity and nucleophilicity 106 6.2.4.4 Local chemical potential and excited states reactivity 107 6.3 Illustrations 108 6.3.1 Woodward Hoffmann rules in Diels-Alder reactions 108 6.3.2 Perturbational MO Theory and Dual descriptor 109 6.3.3 Markovnikov rule 109 6.4 Conclusions 110 References 111 7 Molecular Electrostatic Potentials: Significance and Applications 113 7.1 A Quick Review of Some Classical Physics 113 7.2 Molecular Electrostatic Potentials 113 7.3 The Electronic Density and the Electrostatic Potential 114 7.4 Characterization of Molecular Electrostatic Potentials 115 7.5 Molecular Reactivity 116 7.6 Some Applications of Electrostatic Potentials to Molecular Reactivity 118 7.6.1 σ-Hole and π-Hole Interactions 118 7.6.2 Hydrogen Bonding: A σ-Hole Interaction 119 7.6.3 Interaction Energies 120 7.6.4 Close Contacts and Interaction Sites 121 7.6.5 Biological Recognition Interactions 124 7.6.6 Statistical Properties of Molecular Surface Electrostatic Potentials 125 7.7 Electrostatic Potentials at Nuclei 126 7.8 Discussion and Summary 127 References 127 8 Chemical Reactivity Within the Spin-Polarized Framework of Density Functional Theory 135 8.1 Introduction 135 8.2 The spin-polarized density functional theory as a suitable framework to describe both charge and spin transfer processes 137 8.3 Practical applications of SP-DFT indicators 141 8.4 Concluding remarks and perspectives 145 Acknowledgements 147 References 147 9 Chemical Binding and Reactivity Parameters: A Unified Coarse Grained Density Functional View 167 9.1 Introduction 167 9.2 Theory 169 9.2.1 Concept of electronegativity, chemical hardness, and chemical binding 169 9.2.1.1 Electronegativity and hardness 169 9.2.1.2 Interatomic charge transfer in molecular systems 169 9.2.1.3 Concept of chemical potential and hardness for the bond region 170 9.2.1.4 Spin-polarized generalization of chemical potential and hardness 1
• Edition: 1st
• Publisher Details: Hoboken : John Wiley & Sons, Inc
• Publication Date: 2021
• Extent: 1 online resource
• Subjects: 541.39; Chemical reaction, Conditions and laws of; Chemistry, Physical and theoretical
• Languages: English
• ISBNs: 9781119683230
• Related ISBNs: 9781119684022
• Notes: Note: Description based on CIP data; resource not viewed.
• Access Rights: Legal Deposit; Only available on premises controlled by the deposit library and to one user at any one time; The Legal Deposit Libraries (Non-Print Works) Regulations (UK).
• Access Usage: Restricted: Printing from this resource is governed by The Legal Deposit Libraries (Non-Print Works) Regulations (UK) and UK copyright law currently in force.