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Parts of this thesis have been published in the following journal articles:; Supervisors' Foreword; Acknowledgments; Contents; 1 General Introduction; References; Part I Theoretical Studies in Photophysics and Photochemistry: Applications to Aniline and Pyrazine; 2 Basic Concepts and Methodology; 2.1 The Molecular Schrödinger Equation; 2.1.1 The Molecular Hamiltonian Operator; 2.1.2 The Born
Oppenheimer Approximation; 2.2 Vibronic Coupling; 2.2.1 The Group Born
Oppenheimer Approximation; 2.2.2 The Diabatic Representation; 2.2.3 Conical Intersections
2.3 Basics of Electronic Structure Theory2.3.1 Spin Orbitals and Slater Determinants; 2.3.2 The Hartree
Fock Approximation; 2.3.3 Electronic Correlation; 2.4 Potential Energy Surface Exploration; 2.4.1 Minima and Transition State Optimization; 2.4.2 Minimum Energy Conical Intersection Optimization; 2.4.3 Minimum Energy Paths Optimization; References; 3 Exploration of the Potential Energy Landscape of Aniline Using CASSCF and XMCQDPT2 Electronic Structure Calculations; 3.1 Introduction; 3.1.1 General Trends in the Photochemistry of Simple Aromatic Organic Molecules
3.1.2 Previous Studies on the Photochemistry of Aniline3.2 Computational Details; 3.3 Vertical and Adiabatic Excitation Energies; 3.4 Photochemistry After Excitation to the 1ππ* State; 3.5 Photochemistry After Excitation to the 1πσ* State; 3.6 Photochemistry After Excitation to the 2ππ* State; 3.7 Summary and Conclusions; References; 4 Theory of Nuclear Quantum Dynamics Simulations; 4.1 Setting up the Hamiltonian Operator; 4.1.1 The Choice of the Coordinates and the Nuclear Kinetic Energy Operator; 4.1.2 The Discrete Variable Representation
4.2 The Solution of the Nuclear Time-Dependent Schrödinger Equation4.2.1 The Standard Method; 4.2.2 The Multi-configuration Time-Dependent Hartree Method; 4.2.3 Product Form of the Hamiltonian Operator; 4.2.4 Integration of the Equations of Motion; 4.2.5 The MCTDH Equations of Motion for Several Electronic States; 4.3 The Vibronic Coupling Model; 4.4 Calculation of Absorption Spectra; References; 5 The Role of the Low-Lying nπ* States on the Photophysics of Pyrazine; 5.1 Introduction; 5.2 Ab Initio Electronic Structure Calculations; 5.3 Construction of the Models
5.4 Time-Dependent Nuclear Quantum Dynamics Simulations5.4.1 Simulation of the UV Absorption Spectrum; 5.4.2 Electronic State Populations and Decay Mechanism; 5.5 Conclusion; References; Part II Laser Control of Unimolecular Processes; 6 Theoretical Tools for the Description of Strong Field Laser-Molecule Interaction; 6.1 The Semi-classical Dipolar Approximation of Laser-Matter Interaction; 6.2 Laser Driven Two-Level System; 6.2.1 The Resonant Wave Approximation; 6.2.2 The Rabi Model; 6.2.3 The π-pulse Technique; 6.3 The Non-resonant Dynamic Stark Effect
Oppenheimer Approximation; 2.2 Vibronic Coupling; 2.2.1 The Group Born
Oppenheimer Approximation; 2.2.2 The Diabatic Representation; 2.2.3 Conical Intersections
2.3 Basics of Electronic Structure Theory2.3.1 Spin Orbitals and Slater Determinants; 2.3.2 The Hartree
Fock Approximation; 2.3.3 Electronic Correlation; 2.4 Potential Energy Surface Exploration; 2.4.1 Minima and Transition State Optimization; 2.4.2 Minimum Energy Conical Intersection Optimization; 2.4.3 Minimum Energy Paths Optimization; References; 3 Exploration of the Potential Energy Landscape of Aniline Using CASSCF and XMCQDPT2 Electronic Structure Calculations; 3.1 Introduction; 3.1.1 General Trends in the Photochemistry of Simple Aromatic Organic Molecules
3.1.2 Previous Studies on the Photochemistry of Aniline3.2 Computational Details; 3.3 Vertical and Adiabatic Excitation Energies; 3.4 Photochemistry After Excitation to the 1ππ* State; 3.5 Photochemistry After Excitation to the 1πσ* State; 3.6 Photochemistry After Excitation to the 2ππ* State; 3.7 Summary and Conclusions; References; 4 Theory of Nuclear Quantum Dynamics Simulations; 4.1 Setting up the Hamiltonian Operator; 4.1.1 The Choice of the Coordinates and the Nuclear Kinetic Energy Operator; 4.1.2 The Discrete Variable Representation
4.2 The Solution of the Nuclear Time-Dependent Schrödinger Equation4.2.1 The Standard Method; 4.2.2 The Multi-configuration Time-Dependent Hartree Method; 4.2.3 Product Form of the Hamiltonian Operator; 4.2.4 Integration of the Equations of Motion; 4.2.5 The MCTDH Equations of Motion for Several Electronic States; 4.3 The Vibronic Coupling Model; 4.4 Calculation of Absorption Spectra; References; 5 The Role of the Low-Lying nπ* States on the Photophysics of Pyrazine; 5.1 Introduction; 5.2 Ab Initio Electronic Structure Calculations; 5.3 Construction of the Models
5.4 Time-Dependent Nuclear Quantum Dynamics Simulations5.4.1 Simulation of the UV Absorption Spectrum; 5.4.2 Electronic State Populations and Decay Mechanism; 5.5 Conclusion; References; Part II Laser Control of Unimolecular Processes; 6 Theoretical Tools for the Description of Strong Field Laser-Molecule Interaction; 6.1 The Semi-classical Dipolar Approximation of Laser-Matter Interaction; 6.2 Laser Driven Two-Level System; 6.2.1 The Resonant Wave Approximation; 6.2.2 The Rabi Model; 6.2.3 The π-pulse Technique; 6.3 The Non-resonant Dynamic Stark Effect