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M. Ya. Melnikov, V.A. Smirnov Handbook of Photochemistry of Organic Radicals

M. Ya. Melnikov, V.A. Smirnov
translated by Yu.B. Scheck

Handbook of Photochemistry of Organic Radicals:
Absorption and Emission Properties, Mechanisms, Aging

begell house, 1996

The kinetics and mechanism of reactions involving electronically excited radicals is a division of physical chemistry and high-energy chemistry, which was developed about 30 years ago. Advance in the field is closely related to the solution of fundamental problems of the theory of electronic structure and reactivity as well as of the practical tasks concerning the utilization of flash and laser light sources and the application of various materials in nuclear and aerospace engineering.

To date, an extraordinary amount of experimental data (although sometimes controversial) on the reactions of electronically excited radicals has been compiled in the literature. However, no attempts have been made to summarize this material, which can be explained both by the incompleteness of these studies and by the vagueness of some concepts. In the authors' opinion, the material compiled in the field has to be summarized, and this book is an attempt to do this. In selecting reference materials, the authors focused their attention first of all on the reliable identification of intermediate species by different experimental and theoretical methods because inaccurate assignment can lead to serious errors in interpreting the mechanism of various processes.

For many years, the authors' activities in the field of radical photochemistry have been stimulated by pioneering works of V.V. Voevodskii, N.M. Emanuel, A.L. Buchachenko, V.K. Milinchuk, V.D. Pokhodenko, J. Willard, K. Tsuji, and many others.

We are grateful to our colleagues whose experimental work and fruitful criticism supported us for many years and eventually promoted the appearance of this book.

In conclusion, the authors would like to claim responsibility for possible errors and incorrectness in the text and state that Chapter 6 was written in collaboration with Dr. V.I. Pergushov whereas Chapter 7 was written in the coauthorship of Dr. E.N. Seropegina.


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Contents

1. ABSORPTION AND EMISSION PROPERTIES OF ORGANIC RADICALS AND BIRADICALS1
1.1. Introduction1
1.2. General Characterization of Luminescence from Polyatomic Molecular Systems1
1.2.1. Radiative transitions2
1.2.2. Processes of Radiationless Conversion4
1.3. Electronic Transitions and Absorption Spectra of Aliphatic Radicals5
1.3.1. Alkyl Radicals5
1.3.2. Allyl, Polyene, and Vinyl Radicals11
1.3.3. Alkoxyl Radicals15
1.3.4. Radicals of Alcohols and Ethers16
1.3.5. Acyl Radicals20
1.3.6. Radicals of Esters, Aldehydes, Ketones, Acids, and Anhydrous Acids22
1.3.7. Nitrogen-Containing Radicals25
1.3.8. Sulfur-Containing Radicals32
1.3.9. Peroxide Radicals39
1.3.10. Luminescence Parameters of Small Radicals45
1.4. Absorption and Emission Properties of Aromatic Radicals48
1.4.1. Benzyl Radical48
1.4.2. Benzyl-Type Radicals52
1.4.3. Hydroradicals64
1.4.4. Heteroradicals67
1.4.5. Radical ions70
1.4.6. Biradicals79
1.4.7. Stable Radicals89
2. ELEMENTARY PHOTOCHEMICAL PROCESSES92
2.1. Photodissociation92
2.1.1. Dissociation in Continuum92
2.1.2. Quasi-Equilibrium Dissociation93
2.1.3. Nonadiabatic Dissociation94
2.1.4. Predissociation94
2.1.5. Isotope Effect96
2.2. Photoinduced Intramolecular Electron Transfer97
2.2.1. Charge-Transfer Complex in Ground State100
2.2.2. Exciplexes104
2.2.3. Photoionization of Radicals110
2.2.4. Photoreduction of Radical Cations120
2.3. Photorearrangement121
2.3.1. Conformational Isomerism122
2.3.2. Configurational (cis-trans) Isomerism123
2.3.3. Structural (Valence) Isomerism124
2.4. Photoaddition126
2.5. Transfer of Electronic Energy127
2.6. Intennolecular Quenching in Exchange Complex130
3. PHOTOCHEMISTRY OF ALIPHATIC RADICALS132
3.1. Alkyl Radicals132
3.2. Allyl, Polyene, and Vinyl Radicals137
3.3. Alkoxy Radicals139
3.4. Alcohol and Ester Radicals139
3.S. Acyl Radicals144
3.6. Radicals of Esters, Aldehydes, Ketones, Acids, and Acidic Anhydrides145
3.7. Nitrogen-Containing Radicals150
3.8. Sulfur-Containing Radicals155
3.9. Peroxide Radicals161
4. PHOTOCHEMISTRY OF AROMATIC RADICALS169
4.1. Benzyl-Type Radicals169
4.2. Hydroradicals171
4.3. Heteroradicals173
4.3.1. Phenoxy radicals173
4.3.2. Aminyl radicals181
4.3.3. Stable nitroxyl radicals181
4.4. Biradicals182
4.4.1. Carbenes182
4.4.2. Nitrenes184
4.4.3. Miscellaneous biradicals186
4.5. Radical Ions188
4.6. Quenching of Excited Species201
4.6.1. Quenching of singlet states202
4.6.2. Quenching of triplet states205
4.6.3. Quenching of excited radicals.208
4.6.4. Quenching of the triplet-triplet fluorescence of carbenes212
4.7. Conclusion213
5. QUANTUM YIELDS OF ORGANIC RADICALS IN SOLID PHASE216
6. PHOTORADICAL CHAIN REACTIONS230
7. PHOTORADICAL AGING OF POLYMERS244
7.1. Introduction244
7.2. Pbotoradical Aging of Some Carbo- and Heterochain Polymers246
7.2.1. Polyolefins246
7.2.2. Polystyrene254
7.2.3. Fluorine- and chlorine-containing polymers259
7.2.4. Polyacrylates262
7.2.5. Poly(vinyl acetate), poly(vinyl alcohol), and poly(vinyl acetals)270
7.2.6. Poly(acrylic acid) and poly(acryl amide)281
7.2.7. Polyoxides284
7.2.8. Polyamides and aliphatic polyurethanes286
7.3. Special Features of the Kinetics of Photoradical Reactions in Polymers292
7.4. Means of Controlling the Efficiency and Pathway of Photoradical Reactions in Polymers295
REFERENCES302

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