Introduction 1
Bibliography 1
Part Ⅰ Theoretical Framework 10
Chapter 1 Potential Energy Surfaces 10
1.1 Born-Oppenheimer approximation 12
1.1.1 The total Hamiltonian 12
1.1.2 Adiabatic representation 12
1.1.3 Diabatic representation 14
1.1.4 Diabatic-to-Adiabatic transformation 16
1.1.5 Two-State model 17
1.2 The solution of the electronic problem 18
1.3 Ab initio potential energy surfaces 21
1.3.1 Correlation energy partitioning 23
1.3.2 Semiempirical correction of ab initio energies 24
1.4 Semiempirical global potential energy surfaces 26
1.4.1 Diatomics-in-molecules theory 26
1.4.2 The double many-body expansion method 28
1.4.3 Energy-switching scheme for spectroscopically accurate functions 31
Bibliography 32
Chapter 2 Reaction Dynamics 37
2.1 Classical scattering 42
2.1.1 Molecule collision theory 42
2.1.2 Statistical averaging 46
2.2 The quasiclassical trajectory method 47
2.2.1 Classical Hamiltonian mechanics 47
2.2.2 Coordinate systems and transformations 50
2.2.3 Selection of initial states 52
2.2.4 Integration of the equations of motion 58
2.2.5 Analysis of final states 59
2.2.6 Treatment of the zero-point energy problem 60
2.3 Quantum reaction dynamics:a synopsis 62
2.3.1 The interaction picture 63
2.3.2 Time-dependent approaches 64
2.3.3 Time-independent approaches 66
2.3.4 Reduced dimensionality approaches 69
Bibliography 71
Part Ⅱ Case Studies 80
Chapter 3 Dynamics of the OH(v)+O3(Ev)Atmospheric Reaction 80
Test Studies on the Potential Energy Surface and Rate Constant for the OH+O3 Atmospheric Reaction 81
Dynamics of the OH(v=1,2,4)+O3 Atmospheric Reaction 96
OH(v)+O3:Does Chemical Reaction Dominate over Non-reactive Quenching? 116
Dynamics Study of the OH+O3 Atmospheric Reaction with Both Reactants Vibrationally Excited 131
Vibrational Relaxation of Highly Vibrationally Excited O3 in Collisions with OH 149
Dynamics Study of the Atmospheric Reaction Involving Vibrationally Excited O3 with OH 165
Chapter 4 Dynamics of the O2(v)+HO2(Ev),and HO2+O3 Atmospheric Reaction 187
Dynamics Study of the O2(v)+HO2 Atmospheric Reaction 188
Dynamics of the O2+HO2 Atmospheric Reaction with Both Reactants Vibrationally Excited 212
Vibrational Relaxation of Highly Excited HO2 in Collisions with O2 229
Dynamics of HO2+O3 Reaction Using a Test DMBE Potential Energy Surface:Does It Occur via Oxygen or Hydrogen Atom Abstraction 246