Abstract
Change in intermolecular distance between electron donor (D) and acceptor (A) can induce intermolecular electron transfer (ET) even in nonpolar solvent, where solvent orientational polarization is absent. This was shown by making simple calculations of the energies of the initial and final states of ET. In the case of polar solvent, the free energies are functions of both D-A distance and solvent orientational polarization. On the basis of 2-dimensional free energy surfaces, the relation of Marcus ET and exciplex formation is discussed. The transient effect in fluorescence quenching was measured for several D-A pairs in a nonpolar solvent. The results were analyzed by assuming a distance dependence of the ET rate that is consistent with the above model.
Highlights
Electron transfer (ET) reactions have been studied extensively for many years
In nonpolar solvents, where solvent orientational polarization is absent, ET can occur by the change in intermolecular D-A distance
Intermolecular distance can be regarded as the reaction coordinate of ET reactions
Summary
Electron transfer (ET) reactions have been studied extensively for many years. Fluorescence quenching is often used to study ET reactions involving excited molecules. Two types of ET reactions have been identified in fluorescence quenching: full ET from the electron donor (D) to the acceptor (A) yielding D+ and A− radical ions, and partial ET yielding a fluorescent complex [1] The former mainly occurs in polar environments, and is less important in less polar environments. The latter, on the other hand, mainly occurs in nonpolar and weakly polar environments, and is less important in more polar environments This process is attributed to the formation of the excited-state chargetransfer complex (the exciplex). The relation between Marcus ET and exciplex formation is discussed briefly
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