Physical-Organic Photochemistry. I. Introduction and σ → σ*, π → π* Excitations

  • David Phillips
Part of the NATO Advanced Study Institutes Series book series (NSSA, volume 25)


In the limited time and space available for these topics a coherent resume of organic photochemistry in terms of detailed molecular orbital descriptions is inappropriate. Instead what is offered here are selected topics in physical-organic photochemistry which may be of some interest. As a brief introduction, Figure 1 (over) shows some of the important unimolecular physical and chemical decay paths in a complex polyatomic molecule following S0 → S1 excitation. The quantum yield of any process is defined as the rate of that process relative to the rate of light absorption. For steady-state illumination it is easily shown that, for example, the quantum yield of fluorescence for a molecule undergoing the processes shown in Figure l is where rate-constant subscripts refer to the processes shown in Figure 1.


Quantum Yield Excited Singlet State Bond Dissociation Energy Vibrational Relaxation Rydberg Transition 
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Suggested Further Reading

  1. ‘Excited States in Organic Chemistry’, J.A. Barltrop and J.D. Coyle, Wiley, (Interscience) London, 1975.Google Scholar
  2. ‘Fluorescent Properties of Saturated Systems Hydrocarbons and Amines’, A.M. Halpern, Mol. Photochem., 1973, 5, 517.Google Scholar

Copyright information

© Plenum Press, New York 1979

Authors and Affiliations

  • David Phillips
    • 1
  1. 1.Department of Chemistry, The UniversityUniversity of SouthamptonSouthamptonUK

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