Principles and Applications of Photochemistry

Brian Wardle is the author of Principles and Applications of Photochemistry, published by Wiley.

• Preface xiii1 Introductory Concepts 1Aims and Objectives 11.1 The Quantum Nature of Matter and Light 21.2 Modelling Atoms: Atomic Orbitals 61.3 Modelling Molecules: Molecular Orbitals 91.4 Modelling Molecules: Electronic States 131.5 Light Sources Used in Photochemistry 161.6 Efficiency of Photochemical Processes: Quantum Yield 252 Light Absorption and Electronically-excited States 29Aims and Objectives 292.1 Introduction 292.2 The Beer–Lambert Law 302.3 The Physical Basis of Light Absorption by Molecules 322.4 Absorption of Light by Organic Molecules 352.5 Linearly-conjugated Molecules 392.6 Some Selection Rules 422.7 Absorption of Light by Inorganic Complexes 433 The Physical Deactivation of Excited States 47Aims and Objectives 473.1 Introduction 473.2 Jablonski Diagrams 493.3 Excited-state Lifetimes 534 Radiative Processes of Excited States 59Aims and Objectives 594.1 Introduction 604.2 Fluorescence and Fluorescence Spectra 614.3 An Exception to Kasha’s Rule 634.4 Fluorescence Quantum Yield 644.5 Factors Contributing to Fluorescence Behaviour 654.6 Molecular Fluorescence in Analytical Chemistry 674.7 Phosphorescence 704.8 Delayed Fluorescence 734.9 Lanthanide Luminescence 745 Intramolecular Radiationless Transitions of Excited States 77Aims and Objectives 775.1 Introduction 775.2 The Energy Gap Law 795.3 The Franck–Condon Factor 795.4 Heavy Atom Effects on Intersystem Crossing 825.5 El-Sayed’s Selection Rules for Intersystem Crosssing 836 Intermolecular Physical Processes of Excited States 87Aims and Objectives 876.1 Quenching Processes 886.2 Excimers 906.3 Exciplexes 936.4 Intermolecular Electronic Energy Transfer 966.5 The Trivial or Radiative Mechanism of Energy Transfer 976.6 Long-range Dipole–Dipole (Coulombic) Energy Transfer 986.7 Short-range Electron-exchange Energy Transfer 1056.8 Photoinduced Electron Transfer (PET) 1107 Some Aspects of the Chemical Properties of Excited States 119Aims and Objectives 1197.1 The Pathway of Photochemical Reactions 1207.2 Differences between Photochemical and Thermal Reactions 1247.3 Photolysis 1277.4 An Introduction to the Chemistry of Carbon-centred Radicals 1337.5 Photochemistry of the Complexes and Organometallic Compounds of d-block Elements 1358 The Photochemistry of Alkenes 145Aims and Objectives 1458.1 Excited States of Alkenes 1468.2 Geometrical Isomerisation by Direct Irradiation of C=C Compounds 1478.3 Photosensitised Geometrical Isomerisation of C=C Compounds 1498.4 Concerted Photoreactions 1518.5 Photocycloaddition Reactions 1578.6 Photoaddition Reactions 1599 The Photochemistry of Carbonyl Compounds 161Aims and Objectives 1619.1 Excited States of Carbonyl Compounds 1629.2 α-cleavage Reactions 1639.3 Intermolecular Hydrogen-abstraction Reactions 1669.4 Intramolecular Hydrogen-abstraction Reactions 1679.5 Photocyloaddition Reactions 1689.6 The Role of Carbonyl Compounds in Polymer Chemistry 16910 Investigating Some Aspects of Photochemical Reaction Mechanisms 173Aims and Objectives 17310.1 Introduction 17410.2 Information from Electronic Spectra 17410.3 Triplet-quenching Studies 17610.4 Sensitisation 18010.5 Flash Photolysis Studies 18210.6 Low-temperature Studies 195Further Reading 19611 Semiconductor Photochemistry 197Aims and Objectives 19711.1 Introduction to Semiconductor Photochemistry 19811.2 Solar-energy Conversion by Photovoltaic Cells 19911.3 Semiconductors as Sensitisers for Water Splitting 20411.4 Semiconductor Photocatalysis 20811.5 Semiconductor-photoinduced Superhydrophilicity 211Further Reading 21212 An Introduction to Supramolecular Photochemistry 213Aims and Objectives 21312.1 Some Basic Ideas 21412.2 Host–Guest Supramolecular Photochemistry 21512.3 Supramolecular Photochemistry in Natural Systems 22112.4 Artificial Photosynthesis 22912.5 Photochemical Supramolecular Devices 233Further Reading 238Index 241