Advances in Multi-Photon Processes and Spectroscopy

The following sections are included:

• PREFACE

• CONTENTS

This work presents different experiments of photorelaxation and photodissociation by using either time-dependent treatments based on wave packets propagation or Floquet stationnary matrix theory. Our treatment makes a partioning of the dynamics space explored by the evolution operator and simplifies the relaxation scheme inferred from the Schrödinger equation. The choice of these subspaces and the building up of the effective Hamiltonians which govern the projected dynamics are carried out using Bloch time-dependent or time-independent wave operators technique. The basic equations which feature these wave operators are given. The different recursive solutions based on Jacobi and Gauss-Seidel integration schemes are also included. It is noteworthy that these recent methods can be used to study molecular systems including large basis sets (their dimension may be more than 10⁵ ) and even Hamiltonians dependent explicitly on time. A complete analysis is made of the phenomenon of molecular or electromagnetic field induced resonances. This analysis shows the major role of these resonances in photodissociation processes, raises up the problem linked to their representation on a finite basis set and the difficulties inherent in using time-dependent treatment for scattering experiments.

The following sections are included:

• Introduction

• Experimental Methods
  • Rotational band contour analysis
  • Symmetry reduction as a vibronic level structural probe
  • Frequency shifts and cluster ion fragmentation
  • Dispersed fluorescence scans
  • Fluorescence lifetimes
  • Intermolecular vibrational structure

• Results on the C₆H₆-X Complexes
  • C₆H₆-Ar and C₆H₆-(Ar)₂
  • C₆H₆-HCl
  • C₆H₆-CHCl₃
  • C₆H₆-CCl₄
  • C₆H₆-H₂O
  • C₆-H₆CH₃OH

• The π Hydrogen Bond
  • MMC Calculations on C₆H₆-HCl and C₆H₆-H₂O
  • OPLS Calculations on C₆H₆-CHCl₃ and C₆H₆-CH₃OH
  • Some Comments on the π Hydrogen Bond

• Larger C₆H-X_n Clusters
  • C₆H₆-(H₂O)_n Clusters, n = 2-5
    • C₆H₆-(H₂O)₂
    • C₆H₆-(H₂O)_3-5
  • C₆H₆-(CH₃OH)_m Clusters, m = 2-5
  • C₆H₆-(H₂O)_n (CH₃OH)_m, (n + m) ≤ 4
  • MMC and OPLS calculations on BW_n, BM_m and BW_nM_m

• Concluding Remarks

• Acknowledgements

• References

The following sections are included:

• INTRODUCTION

• THE SYSTEM-RESERVOIR MODEL AND THE CLASSICAL AND QUANTUM THEORIES OF RELAXATION
  • Classical system-reservoir theory
  • Quantum theory of system-reservoir interaction: the master equation

• GENERALIZATIONS OF THE MASTER EQUATION
  • Master equation for nonlinear systems
    • The master equation
    • Applications
  • Master equation for systems driven by ultrastrong field
    • The master equation
    • Application: Field-dependent relaxation
  • Non-Markovian master equation for linear systems
    • The basic equation
    • Applications
  • Non-Markovian master equation for nonlinear systems
    • Application
  • Master equation for systems stochastically perturbed
    • The basic equation
    • Applications
  • Master equation for reservoirs prepared in correlated states
    • The model and the basic equation
    • Applications
  • The master equation for squeezed reservoirs
    • The basic equations
    • Applications
    • Master equation for phase-sensitive reservoirs

• An Overview of Some Related Developments

• Conclusion

• Acknowledgements

• References

• Figures

The following sections are included:

• Introduction

• Surface Nonlinear Optical Signals
  • Signal Generation
  • The Signal Strength

• The Surface Nonlinear Susceptibility
  • Surface selectivity
  • Symmetry, structure and adsorbate orientation
    • Determination Of
    • The Determination Of Adsorbate Orientation
  • Resonance Enhancement and Spectroscopy

• Kinetic Studies by SHG and SFG
  • Quasi-Steady State Measurements
    • Adsorption Kinetics
    • Electrochemical Interfaces
    • Photochemical Reactions At Interfaces
    • Thermally Induced Surface Reactions
    • Phase Transitions In Insoluble Monolayers
    • Adsorbate Diffusion By Monolayer Grating Scattering
  • Ultrafast Adsorbate Dynamics
    • Vibrational Relaxation In Adsorbates
    • Excited State Dynamics Of Adsorbates
    • Desorption Dynamics
    • Coherent Processes At Interfaces
    • Structural Dynamics Of Surfaces

• Summary and Prospects

• Acknowledgement

• References

In the present paper several measuring methods of femtosecond time-resolved nonlinear response newly developed mainly by the author's group are presented. It contains methods using time incoherent light and coherent short pulse. Both of them can be utilized for the Kerr dynamics of liquids, electronic dephasing, vibrational dephasing, and depopulation processes with femtosecond resolution. They can be used for the determination of femtosecond-resolved complex third-order nonlinear susceptibility with spectral resolution. Several examples of experiments which demonstrate the usefulness of those methods are also described.