Modern Aspects of Diffusion-Controlled Reactions (eBook)
611 Seiten
Elsevier Science (Verlag)
978-0-08-053667-5 (ISBN)
The book demonstrates that incorporation of the reaction-induced spatial correlations of similar reactants (e.g., vacancy-vacancy) leads to the development of an essentially non-Poisson spectrum of reactant density fluctuations. This can completely change the kinetics at longer times since it no longer obeys the law of mass action. The language of the correlation lengths and critical exponents similar to physics of critical phenomena is used instead. A relation between MPD theory and synergistics is discussed. The validity of the theorem giving a critical complexity for the two-step reactions exhibiting self-organization phenomena is questioned. Theoretical results are illustrated by numerous experimental data.
This monograph deals with the effects of reactant spatial correlations arising in the course of basic bimolecular reactions describing defect recombination, energy transfer and exciton annihilation in condensed matter. These effects lead to the kinetics considered abnormal from the standard chemical kinetics point of view. Numerous bimolecular reaction regimes and conditions are analysed in detail. Special attention is paid to the development and numerous applications of a novel, many-point density (MPD) formalism, which is based on Kirkwood's superposition approximation used for decoupling three-particle correlation functions.The book demonstrates that incorporation of the reaction-induced spatial correlations of similar reactants (e.g., vacancy-vacancy) leads to the development of an essentially non-Poisson spectrum of reactant density fluctuations. This can completely change the kinetics at longer times since it no longer obeys the law of mass action. The language of the correlation lengths and critical exponents similar to physics of critical phenomena is used instead. A relation between MPD theory and synergistics is discussed. The validity of the theorem giving a critical complexity for the two-step reactions exhibiting self-organization phenomena is questioned. Theoretical results are illustrated by numerous experimental data.
Front Cover 1
Modern Aspects of Diffusion-Controlled Reactions: Cooperative Phenomena in Bimolecular Process 4
Copyright Page 5
Contents 18
Preface 10
Chapter 1. Guide to the book 26
1.1 What is this book written for? 26
1.2 Order and disorder 29
1.3 How many particles are necessary to create a many-particle problem? 37
1.4 Intermediate order 50
1.5 Critical phenomena 56
References 76
Chapter 2. Basic methods for describing chemical kinetics in condensed media: continuum models 78
2.1 Macroscopic approach 78
2.2 The treatment of stochasticity on a mesoscopic level 109
2.3 Microscopic treatment of stochasticity 133
References 159
Chapter 3. From pair kinetics toward the many-reactant problem 164
3.1 Basic defects and processes in solids 164
3.2 Annealing of geminate pairs of defects 174
References 192
Chapter 4. The linear approximation in bimolecular reaction kinetics 196
4.1 The shortened superposition approximation (A + B -» 0 reaction) 196
4.2 Tunnelling recombination 213
4.3 Non-diffusion defect recombination and non-stationary kinetics 232
References 255
Chapter 5. The fluctuation-controlled kinetics: the basic formalism of many-point particle densities 260
5.1 The A + B —> 0 reaction
5.2 The A + B —> B reaction
5.3 The A + A —> 0 and A + A —>
References 321
Chapter 6. The many-particle effects in irreversible A + B -> 0 reaction
6.1 Long-range recombination of immobile particles 326
6.2 Kinetics of diffusion-controlled reactions of mobile non-interacting particles 355
6.3 Dynamic particle aggregation induced by elastic interactions 381
6.4 Effect of non-equilibrium charge screening (Coulomb interaction) 396
References 408
Chapter 7. The many-particle effects in A + B —> 0 reaction with particle generation
7.1 The kinetics of defect accumulation under irradiation 412
7.2 Diffusion-controlled particle aggregation under permanent source 440
7.3 Other approaches 454
7.4 Probabilistic models and computer simulations 463
References 486
Chapter 8. Systems under birth and death conditions: Lotka and Lotka–Volterra models 492
8.1 A novel criterion of the marginal complexity insuring self-organization in the course of chemical reactions 492
8.2 The Lotka–Volterra model 498
8.3 The Lotka model 518
References 537
Chapter 9. Catalytic reactions on solid surfaces 540
9.1 A stochastic model for surface reactions without energetic interactions 540
9.2 A stochastic model for surface reactions including energetic particle interactions 589
References 616
Chapter 10. General conclusion 618
References 619
Author Index 622
Subject Index 632
Erscheint lt. Verlag | 24.10.1996 |
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Sprache | englisch |
Themenwelt | Naturwissenschaften ► Chemie ► Physikalische Chemie |
Naturwissenschaften ► Chemie ► Technische Chemie | |
Naturwissenschaften ► Physik / Astronomie ► Festkörperphysik | |
Naturwissenschaften ► Physik / Astronomie ► Thermodynamik | |
Technik ► Maschinenbau | |
ISBN-10 | 0-08-053667-0 / 0080536670 |
ISBN-13 | 978-0-08-053667-5 / 9780080536675 |
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