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Handbook of Photochemistry of Organic Radicals:

ISBN:
1-56700-071-1 (Imprimer)

Handbook of Photochemistry of Organic Radicals:

Description

The kinetics and mechanisms of reactions involving electronically excited radicals is a division of physical chemistry and high-energy chemistry, and was developed about 30 years ago. Advances in the field are closely related to the solution of fundamental problems concerning the theory of electronic structure and reactivity, as well as the practical tasks of using flash and laser light sources and the application of various materials in nuclear and aerospace engineering. To date, an extraordinary amount of experimental data (sometimes controversial) on the reactions of electronically excited radicals has been reported in the literature. However, no attempts have been made to summarize all this material for practical use until the publication of this volume.



355 pages, © 1996

Table des matières:

Foreword
Nomenclature
1. ABSORPTION AND EMISSION PROPERTIES OF ORGANIC RADICALS AND BIRADICALS
1.1. Introduction
1.2. General Characterization of Luminescence from Polyatomic Molecular Systems
1.2.1. Radiative transitions
1.2.2. Processes of Radiationless Conversion
1.3. Electronic Transitions and Absorption Spectra of Aliphatic Radicals
1.3.1. Alkyl Radicals
1.3.2. Allyl, Polyene, and Vinyl Radicals
1.3.3. Alkoxyl Radicals
1.3.4. Radicals of Alcohols and Ethers
1.3.5. Acyl Radicals
1.3.6. Radicals of Esters, Aldehydes, Ketones, Acids, and Anhydrous Acids
1.3.7. Nitrogen-Containing Radicals
1.3.8. Sulfur-Containing Radicals
1.3.9. Peroxide Radicals
1.3.l0. Luminescence Parameters of Small Radicals
1.4. Absorption and Emission Properties of Aromatic Radicals
1.4.1. Benzyl Radical
1.4.2. Benzyl-Type Radicals
1.4.3. Hydroradicals
1.4.4. Heteroradicals
1.4.5. Radical ions
1.4.6. Biradicals
1.4.7. Stable Radicals
2. ELEMENTARY PHOTOCHEMICAL PROCESSES
2.1. Photodissociation
2.1.1. Dissociation in Continuum
2.1.2. Quasi-Equilibrium Dissociation
2.1.3. Nonadiabatic Dissociation
2.1.4. Predissociation
2.1.5. Isotope Effect
2.2. Photoinduced Intramolecular Electron Transfer
2.2.1. Charge-Transfer Complex in Ground State
2.2.2. Exciplexes
2.2.3. Photoionization of Radicals
2.2.4. Photoreduction of Radical Cations
2.3. Photorearrangement
2.3.1. Conformational Isomerism
2.3.2. Configurational (cis-trans) Isomerism
2.3.3. Structural (Valence) Isomerism
2.4. Photoaddition
2.5. Transfer of Electronic Energy
2.6. Intermolecular Quenching in Exchange Complex
3. PHOTOCHEMISTRY OF ALIPHATIC RADICALS
3.1. Alkyl Radicals
3.2. Allyl, Polyene, and Vinyl Radicals
3.3. Alkoxy Radicals
3.4. Alcohol and Ester Radicals
3.5. Acyl Radicals
3.6. Radicals of Esters, Aldehydes, Ketones, Acids, and Acidic Anhydrides
3.7. Nitrogen-Containing Radicals
3.8. Sulfur-Containing Radicals
3.9. Peroxide Radicals
4. PHOTOCHEMISTRY OF AROMATIC RADICALS
4.1. Benzyl-Type Radicals
4.2. Hydroradicals
4.3. Heteroradicals
4.3.1. Phenoxy radicals
4.3.2. Aminyl radicals
4.3.3. Stable nitroxyl radicals
4.4. Biradicals
4.4.1. Caibenes
4.4.2. Nitrenes
4.4.3. Miscellaneous biradicals
4.5. Radical Ions
4.6. Quenching of Excited Species
4.6.1. Quenching of singlet states
4.6.2. Quenching of triplet states
4.6.3. Quenching of excited radicals
4.6.4. Quenching of the triplet-triplet fluorescence of carbenes
4.7. Conclusion
5. QUANTUM YIELDS OF ORGANIC RADICALS IN SOLID PHASE
6. PHOTORADICAL CHAIN REACTIONS
7. PHOTORADICAL AGING OF POLYMERS
7.1. Introduction
7.2. Photoradical Aging of Some Carbo- and Heterochain Polymers
7.2.1. Polyolefins
7.2.2. Polystyrene
7.2.3. Fluorine- and chlorine-containing polymers
7.2.4. Polyaciylates
7.2.5. Poly(vinyl acetate), poly(vinyl alcohol), and poly(vinyl acetals)
7.2.6. Poly(aciylic acid) and poly(aciyl amide)
7.2.7. Polyoxides
7.2.8. Polyamides and aliphatic polyurethanes
7.3. Special Features of the Kinetics of Photoradical Reactions in Polymers
7.4. Means of Controlling the Efficiency and Pathway of , Photoradical Reactions in Polymers
References