Table of Contents

1. Introduction.

1.1 Who’s Afraid Of Photochemistry?

1.2 Electromagnetic Radiation.

1.3 Perception Of Colour.

1.4 Electronic States: Elements Of Molecular Quantum Mechanics.

1.5 Problems.

2. A Crash Course In Photophysics And A Classification Of Primary Photoreactions.

2.1 Photophysical Processes.

2.2 Energy Transfer, Quenching and Sensitization.

2.3 A Classification of Photochemical Reaction Pathways.

2.4 Problems.

3. Techniques And Methods.

3.1 Light Sources, Filters, and Detectors.

3.2 Preparative Irradiation.

3.3 Absorption Spectra.

3.4 Steady-State Emission Spectra and Their Correction.

3.5 Time-Resolved Luminescence.

3.6 Absorption And Emission Spectroscopy With Polarized Light.

3.7 Flash Photolysis.

3.8 Time-Resolved IR and Raman Spectroscopy.

3.9 Quantum Yields.

3.10 Low-Temperature Studies; Matrix Isolation.

3.11 Photoacoustic Calorimetry.

3.12 Two-Photon Absorption Spectroscopy.

3.13 Single-Molecule Spectroscopy.

3.14 Problems.

4. Quantum Mechanical Models of Electronic Excitation and Photochemical Reactivity.

4.1 Boiling Down The Schr™Dinger Equation.

4.2 Hšckel Molecular Orbital Theory.

4.3 HMO Perturbation Theory.

4.4 Symmetry Considerations.

4.5 Simple Quantum Chemical Models of Electronic Excitation.

4.6 Pairing Theorems and Dewar’s PMO Theory.

4.7 The Need for Improvement; SCF, CI And DFT Calculations.

4.8 Spin-Orbit Coupling.

4.9 Theoretical Models of Photoreactivity, Correlation Diagrams.

4.10 Problems.

4.11 Appendix.

5. Photochemical Reaction Mechanisms and Reaction Intermediates.

5.1 What is a Reaction Mechanism?

5.2 Electron Transfer.

5.3 Proton Transfer.

5.4 Primary Photochemical Intermediates: Examples and Concepts.

5.5 Photoisomerization of Double Bonds.

5.6 Chemiluminescence and Bioluminescence.

5.7 Problems.

6. Chemistry Of Excited Molecules.

6.1 Alkenes And Alkynes.

6.2 Aromatic Compounds.

6.3 Oxygen Compounds.

6.4 Nitrogen Compounds.

6.5 Sulphur Compounds.

6.6 Halogen Compounds.

6.7 Molecular Oxygen.

6.8 Photosensitizers, Photoinitiators and Photocatalysts.

7. Retrosynthetic Photochemistry.

8. Information Sources, Tables.

9. Index.

10. References.

About the Author

Petr Klán is Professor of Organic Chemistry in the Department of Chemistry, Masaryk University, Brno, Czech Republic.

Jakob Wirz is Professor of Physical Chemistry in the Department of Chemistry, University of Basel, Switzerland.