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2.3.4 Three-Body Electron-Ion Recombination 40
2.3.5 Radiative Electron-Ion Recombination 42
2.4 Electron Losses due to Formation of Negative Ions: Electron Attachment and Detachment
Processes
42
2.4.1 Dissociative Electron Attachment to Molecules 43
2.4.2 Three-Body Electron Attachment to Molecules 46
2.4.3 Other Mechanisms of Formation of Negative Ions 47
2.4.4 Mechanisms of Negative Ion Destruction: Associative Detachment Processes 48
2.4.5 Electron Impact Detachment 50
2.4.6 Detachment in Collisions with Excited Particles 51
2.5 Ion-Ion Recombination Processes 52
2.5.1 Ion-Ion Recombination in Binary Collisions 52
2.5.2 Three-Body Ion-Ion Recombination: Thomson’s Theory 55
2.5.3 High-Pressure Limit of Three-Body Ion-Ion Recombination: Langevin Model 56
2.6 Ion-Molecular Reactions 58
2.6.1 Ion-Molecular Polarization Collisions: Langevin Rate Coefficient 58
2.6.2 The Ion-Atom Charge Transfer Processes 61
2.6.3 Nonresonant Charge Transfer Processes 64
2.6.4 Ion-Molecular Reactions with Rearrangement of Chemical Bonds 65
2.6.5 Ion-Molecular Chain Reactions and Plasma Catalysis 66
2.6.6 Ion-Molecular Processes of Cluster Growth: the Winchester Mechanism 67
Problems and Concept Questions 69
Chapter
3
Elementary Processes of Excited Molecules and Atoms in Plasma 73
3.1 Electronically Excited Atoms and Molecules in Plasma 73
3.1.1 Electronically Excited Particles: Resonance and Metastable States 74
3.1.2 Electronically Excited Atoms 74
3.1.3 Electronic States of Molecules and Their Classification 77
3.1.4 Electronically Excited Molecules and Metastable Molecules 78
3.2 Vibrationally and Rotationally Excited Molecules 81
3.2.1 Potential Energy Curves for Diatomic Molecules: Morse Potential 81
3.2.2 Vibration of Diatomic Molecules: Model of Harmonic Oscillator 84
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3.2.3 Vibration of Diatomic Molecules: Model of Anharmonic Oscillator 86
3.2.4 Vibrationally Excited Polyatomic Molecules: the Case of Discrete Vibrational Levels 88
3.2.5 Highly Vibrationally Excited Polyatomic Molecules: Vibrational Quasi Continuum 92
3.2.6 Rotationally Excited Molecules 94
3.3 Elementary Processes of Vibrational, Rotational, and Electronic Excitation of Molecules in Plasma 96
3.3.1 Vibrational Excitation of Molecules by Electron Impact 96
3.3.2 Lifetime of Intermediate Ionic States during Vibrational Excitation 97
3.3.3 Rate Coefficients of Vibrational Excitation by Electron Impact: Semiempirical Fridman’s
Approximation
100
3.3.4 Rotational Excitation of Molecules by Electron Impact 101
3.3.5 Electronic Excitation of Atoms and Molecules by Electron Impact 103
3.3.6 Rate Coefficients of Electronic Excitation in Plasma by Electron Impact 104
3.3.7 Dissociation of Molecules by Direct Electron Impact 106
3.3.8 Distribution of Electron Energy in Nonthermal Discharges between Different Channels of Excitation
and Ionization
107
3.4 Vibrational (VT) Relaxation; the Landau-Teller Formula 113
3.4.1 Vibrational-Translational (VT) Relaxation: Slow Adiabatic Elementary Process 113
3.4.2 Quantitative Relations for Probability of the Elementary Process of Adiabatic VT Relaxation 115
3.4.3 VT Relaxation Rate Coefficients for Harmonic Oscillators: Landau-Teller Formula 117
3.4.4 Vibrational VT Relaxation of Anharmonic Oscillators 119
3.4.5 Fast Nonadiabatic Mechanisms of VT Relaxation 121
3.4.6 VT Relaxation of Polyatomic Molecules 122
3.4.7 Effect of Rotation on the Vibrational Relaxation of Molecules 124
3.5 Vibrational Energy Transfer between Molecules: VV Relaxation Processes 125
3.5.1 Resonant VV Relaxation 125
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