Contents

• Introduction
  • Chemistry in water
  • Theoretical chemistry
  • Our model
  • This thesis
  
  
• Techniques
  • Statistical thermodynamics
  • Reaction rate theory
  • Car-Parrinello molecular dynamics
  • Density Functional Theory
  
  
• Solvation effects on the S2 reaction between CHCl and Cl, in water
  • Introduction
  • Method
    • Density Functional and Molecular Dynamics Method
    • Free energy calculation
    • Gas phase computations
    • Aqueous solution computations
  • Results
    • Structures and energies of isolated compounds
    • Water and hydrochloric acid
    • S2 reaction in gas phase
    • S2 reaction in water
  • Discussion
  • Conclusions
  • Acknowledgment
  • Appendix A: Force of constraint
  • Appendix B: Reaction rate
  • Appendix C: Coordination constraint as the reaction coordinate
  
  
• A Car-Parrinello study of the formation of oxidizing intermediates from Fenton's reagent in aqueous solution
  • Introduction
  • Methodology
    • Fe + 2 Cl in water
  • Results
    • Energetics of OH. versus Fe(IV)O formation in vacuo
    • Starting from hydrogen peroxide coordinated to Fe
    • Internal H-bond in Fe-HO complex
    • HO coordinating to and reacting with Fe
  • Summary and conclusions
  • Acknowledgement
  
  
• Fenton-like chemistry in water: oxidation catalysis by Fe(III) and HO
  • Introduction
  • Computational Details
  • Results
    • Elementary Fenton and Fenton-like reactions in vacuo
    • The first reaction step in Fenton-like chemistry in water: formation and characterization of the iron(III) hydroperoxo species
    • The second step in Fenton-like chemistry in water: calculation of the free energy barrier of O-O homolysis of Fe(III)OOH
  • Conclusions
  • Acknowledgements
  
  
• Reaction path sampling of the reaction between iron(II) and hydrogen peroxide in aqueous solution
  • Introduction
  • Initial reaction path
  • Computational details
  • Transition path sampling
  • Results
    • Determination of the transition state on the initial reaction path
    • Transition path sampling
  • Discussion
  • Conclusion
  • Acknowledgements
  
  
• Methane oxidation by the ferryl ion
  • Introduction
  • Method
  • Gas Phase Calculations
    • The methane coordination mechanism
    • Rebound mechanism
  • H-abstraction from methane by iron(IV)oxo in water
  • Conclusion
  • Acknowledgements
  
  
• Summary
• Nederlandstalige samenvatting
• Dankwoord
• Publications
• About the author
• About the simulation movies in this thesis
• Bibliography
• About this document ...