Theory of Electronic Energy Transfer

  • Walter S. Struve
Chapter
Part of the Advances in Photosynthesis and Respiration book series (AIPH, volume 2)

Summary

This chapter deals with theoretical mechanisms for electronic excitation transfer among photosynthetic pigments. General multipole expansions of intermolecular electrostatic potential energies are described in detail. We review the Golden Rule derivation of the Förster-Dexter theory for dipole-dipole and exchange transfer in the weak-coupling limit; emphasis is placed on its underlying assumptions and limitations. Extension of the Golden Rule to higher-order perturbation theory permits the description of spin-forbidden (e.g. singlet-triplet) energy transfer, as well as remote heavy-atom effects on intersystem crossing. The concepts of the density operator and density matrix are introduced. We demonstrate the need for a unified energy transfer theory that treats coherence as well as excited state population decay. The stochastic Liouville equations (SLE) are solved for the prototype case of a strongly interacting pair of chromophores, and expressions are obtained for the time-dependent anisotropy r(t) in optical fluorescence and pump-probe experiments in strongly coupled systems. While time-dependent SLE solutions are required to predict anisotropy decays, evaluation of the initial anisotropy r(0) requires only knowledge of the excitation conditions and the exciton component transition moments. Current techniques are described for the simulation of temperature dependence in Förster energy transfer rates, via the influence of electron-phonon and electron-vibration coupling on pigment absorption and fluorescence spectra.

Abbreviations

FMO - Fenna-Matthews-Olson bacterio-chlorophyll protein RHAE - remote heavy atom effect SLE - stochastic Liouville equation 
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Copyright information

© Kluwer Academic Publishers 1995

Authors and Affiliations

  • Walter S. Struve
    • 1
  1. 1.Ames Laboratory-USDOE and Department of ChemistryIowa State UniversityAmesUSA

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