Photoinduced electron transfer (PET) is a term reserved to describe the transfer of an electron between photoexcited and ground-state molecules. The energetics and dynamics of PET are shown to depend on the structure of the reactants, the distance separating the reactants, the nature and polarity of the medium, and Coulombic effects. The dynamic interplay of these parameters gives rise to a variety of intermediates, including short-lived Franck-Condon intermediates, exciplexes, contact ion pairs, solvent-separated radical ions, and free ions. An understanding of the spin dynamics of PET can be helpful in sorting out various charge intermediates. The rate of PET is explored on the basis of the classical Marcus-Hush theory and nonclassical, quantum mechanical theories. Special attention is given to the role of electronic and nuclear barriers. A discussion of various procedures used to maximize the efficiency of ion-pair formation is presented, with attention to recent examples.
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