Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
2 General Kinetic Rules for Chemical Reactions, Collisional,
and Intramolecular Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5
2.1 Rates of Reaction, Collisional, and Spontaneous Processes.
Rate Constants. Kinetic Types of Simple Processes . . . . . . . . . . .
5
2.1.1 Kinetic Types of Simple Processes . . . . . . . . . . . . . . . . . . 11
2.2 Chemical Equilibrium. Equilibrium Constant . . . . . . . . . . . . . . . . 13
2.3 Arrhenius Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.4 Complex Reactions. Consecutive Reactions. Steady-State
Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.4.1 Steady-State Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3 Theory of Elementary Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1 Cross-Sections, Rate Constants, and Probabilities of Elementary
Processes. The Detailed Balance Principle . . . . . . . . . . . . . . . . . . 37
3.2 Adiabatic Approximations. Potential Energy Curves
and Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.3 Intermolecular Interactions. Types of Intermolecular
Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.3.1 Exchange Interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.3.2 Direct Electrostatic Interactions . . . . . . . . . . . . . . . . . . . . 50
3.3.3 Polarization Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.3.4 Resonance Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.4 Semiempirical Model Potentials for Intermolecular
Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.5 Descriptions of Collisional Processes Using Potential Energy
Curves and Surfaces. Intramolecular Vibrational Relaxation
in Polyatomic Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
ix
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
2 General Kinetic Rules for Chemical Reactions, Collisional,
and Intramolecular Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5
2.1 Rates of Reaction, Collisional, and Spontaneous Processes.
Rate Constants. Kinetic Types of Simple Processes . . . . . . . . . . .
5
2.1.1 Kinetic Types of Simple Processes . . . . . . . . . . . . . . . . . . 11
2.2 Chemical Equilibrium. Equilibrium Constant . . . . . . . . . . . . . . . . 13
2.3 Arrhenius Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.4 Complex Reactions. Consecutive Reactions. Steady-State
Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.4.1 Steady-State Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3 Theory of Elementary Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1 Cross-Sections, Rate Constants, and Probabilities of Elementary
Processes. The Detailed Balance Principle . . . . . . . . . . . . . . . . . . 37
3.2 Adiabatic Approximations. Potential Energy Curves
and Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.3 Intermolecular Interactions. Types of Intermolecular
Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.3.1 Exchange Interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.3.2 Direct Electrostatic Interactions . . . . . . . . . . . . . . . . . . . . 50
3.3.3 Polarization Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.3.4 Resonance Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.4 Semiempirical Model Potentials for Intermolecular
Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.5 Descriptions of Collisional Processes Using Potential Energy
Curves and Surfaces. Intramolecular Vibrational Relaxation
in Polyatomic Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
ix