This book is devoted to the systematic treatment of nonequi 1 ibrium vibrational kinetics in molecular systems. Particular emphasis is given to the vibrational excitation of diatomic molecules by low-energy electrons in a discharge and by IR photons in laser-pumped systems. The book follows the different steps of the introduction, redistribution, loss, and chemical conversion of the vibrational quanta, from the points of view of the overall kinetics and the dynamics of elementary processes. These two aspects are balanced in a multidisciplinary approach. The different chapters give the basic instruments (theoretical and experimental) which are needed to understand the ki netics of nonequilibrium systems. The book will introduce the reader to different areas such as plasmachemistry, laser chemistry, IR and Raman spectroscopy, and relaxation phenomena, emphasizing how the vibrational energy affects such research fields. The chapters dedicated to collisional dynamics involving vibrational excited molecules provide an introduc tion to the modern techniques uti 1 ized in the scattering theory of inelastic and reactive collisions. The extension of the vibrational kinetics to polyatomic mole cules, discussed in Chap. 10, is the natural bridge between coll ision and coll i sionless regimes. In conclusion, we hope that the approach followed in this book will stimulate the collaboration of researchers coming from different research fields, which are too often completely separate.

Inhalt

1. Introduction.- 1.1 Nonequilibrium Versus Equilibrium Vibrational Kinetics.- 1.2 Organization of This Book.- 2. Vibrational Kinetics, Dissociation, and Ionization of Diatomic Molecules Under Nonequilibrium Conditions.- 2.1 Laser-Induced Vibrational Kinetics.- 2.2 Nonequilibrium Vibrational Kinetics Under Electrical Discharges.- 2.3 Post-Discharge Conditions.- 2.4 Summary.- References.- 3. Analytical Theory of Vibrational Kinetics of Anharmonic Oscillators.- 3.1 Historical Overview.- 3.2 Rate Equations and Probabilities of Elementary Processes.- 3.3 V-T Relaxation in an Inert Gas.- 3.4 Treanor Distribution in the V-V Exchange.- 3.5 V-V and V-T Exchange. Weak Excitation Regime.- 3.6 Resonance V-V Relaxation Under High-Excitation Conditions. Steady-State Conditions.- 3.7 Relaxation at Moderate Excitation of Vibrations.- 3.8 Non-Steady-State Relaxation Regime at High Excitation.- 3.9 Vibrational Kinetics and Chemical Reactions Involving Vibrational1y Excited Molecules.- 3.10 Laser Emission Excitation of Molecular Vibrations.- 3.11 Vibrational Relaxation Under Adiabatic Expansion in the Supersonic Nozzle.- 3.12 Further Studies and Outlook.- References.- 4. Vibration-Vibration and Vibration-Translation Energy Transfer, Including Multiquantum Transitions in Atom-Diatom and Diatom-Diatom Collisions.- 4.1 First-Order Theories.- 4.2 Scaling Theories.- 4.3 Semiclassical Theories.- 4.4 Analytical Expressions for V-V and V-T Rate Constants.- 4.5 Energy Transfer in Specific Systems.- 4.A Appendix: Tables of Energy Transfer Rates in the H2 + H2, N2 + N2, He + CO, and CO + CO Systems.- References.- 5. Vibrational Energy Transfer in Collisions Involving Free Radicals.- 5.1 Mechanisms for Vibrational Relaxation.- 5.2 Experimental Results and Discussion.- 5.3 Conclusion and Prognosis.-References.- 6. Dynamics of Reactions Involving Vibrationally Excited Molecules.- 6.1 Experimental and Computational Results for Representative Atom-Diatom Reactions.- 6.2 Theoretical Outlook.- 6.3 Conclusions.- References.- 7. Vibrational Excitation and Dissociative Attachment.- 7.1 The Resonance Model.- 7.2 Applications to Specific Molecules.- 7.3 Applications of the Attachment Process Under Nonequilibrium Conditions.- 7.A Appendix: Normalization of Continuum Functions.- References.- 8. Vibrational Distribution and Rate Constants for Vibrational Energy Transfer.- 8.1 Vibrational Distribution.- 8.2 Rate Constants for Vibrational Energy Transfer.- References.- 9. Isotope Separation by Vibration-Vibration Pumping.- 9.1 Kinetic Modeling.- 9.2 Experimental Studies.- 9.3 V-V Pumping as an Alternative Method of Stable Isotope Preparation.- References.- 10. Vibrational Kinetics and Reactions of Polyatomic Molecules in Nonequilibrium Systems.- 10.1 Elementary Process of V-T Relaxation of Highly Excited Polyatomic Molecules.- 10.2 Elementary Process of V-V Exchange of Highly Excited Polyatomic Molecules.- 10.3 Population of Vibrationally Excited States of Polyatomic Molecules in Nonequilibrium Conditions.- 10.4 Reactions of Polyatomic Molecules Under Essentially Nonequilibrium Conditions.- 10.5 CO2 Dissociation Stimulated by Vibrational Excitation of Molecules in Plasma.- 10.6 Summary.- References.- 11. Coupling of Vibrational and Electronic Energy Distributions in Discharge and Post-Discharge Conditions.- 11.1 Coupling Between NV and the Free-Electron Energy Distribution Function.- 11.2 Coupling Between NV and NV*.- 11.3 Conclusions.- References.- Additional References with Titles.