Quantum Dynamics and Laser Control for Photochemistry

1. Front Matter

   Pages i-xiii

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2. General Introduction

   • Matthieu Sala

   Pages 1-10

3. Theoretical Studies in Photophysics and Photochemistry: Applications to Aniline and Pyrazine

   1. Front Matter

      Pages 11-11

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   2. Basic Concepts and Methodology

      • Matthieu Sala

      Pages 13-40

   3. Exploration of the Potential Energy Landscape of Aniline Using CASSCF and XMCQDPT2 Electronic Structure Calculations

      • Matthieu Sala

      Pages 41-65

   4. Theory of Nuclear Quantum Dynamics Simulations

      • Matthieu Sala

      Pages 67-86

   5. The Role of the Low-Lying \(n\pi ^*\) States on the Photophysics of Pyrazine

      • Matthieu Sala

      Pages 87-104

4. Laser Control of Unimolecular Processes

   1. Front Matter

      Pages 105-105

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   2. Theoretical Tools for the Description of Strong Field Laser-Molecule Interaction

      • Matthieu Sala

      Pages 107-127

   3. Laser Control of the Radiationless Decay in Pyrazine Using the Dynamic Stark Effect

      • Matthieu Sala

      Pages 129-148

   4. Laser Driven Tunneling Dynamics in NHD\(_2\)

      • Matthieu Sala

      Pages 149-184

   5. Conclusion

      • Matthieu Sala

      Pages 185-189

The central subject of this thesis is the theoretical description of ultrafast dynamical processes in molecular systems of chemical interest and their control by laser pulses. This work encompasses different cutting-edge methods in quantum chemistry, quantum dynamics and for the rigorous description of the interaction of light and matter at the molecular level. It provides a general quantum mechanical framework for the description of chemical processes guided by laser pulses, in particular near conical intersections, i.e. geometries where the nuclear and electronic motions couple and the molecule undergoes non-adiabatic (or non-Born-Oppenheimer) dynamics. In close collaboration with experimentalists, the author succeeds in making a decisive step to link and to apply quantum physics to chemistry by transferring state of the art techniques and concepts developed in physics to chemistry, such as “light dressed atoms and molecules” and “adiabatic Floquet theory”. He applies these techniques in three prototypic model systems (aniline, pyrazine and NHD2) using high-level electronic structure calculations. Readers will enjoy the comprehensive and accessible introduction to the topic and methodology, as well as the clear structure of the thesis.

• Molecular quantum dynamics
• Adiabatic Floquet theory
• Conical intersections
• Ultrafast dynamical processes
• Photochemical dynamics
• Laser control of molecular processes
• Photophysical processes
• Excited state dynamics
• Molecular tunneling dynamics
• Potential energy surfaces
• Dark and bright states
• Non-resonant laser pulses
• Non-resonant dynamic Stark effect

• Interdisciplinaire Carnot de Bourgogne, Université de Bourgogne; Laboratoire, Kiel, Germany

  Matthieu Sala

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