two-dimensional free energy surfaces for electron transfer reactions in solution
;Shigeo Murata;Maged El-Kemary;M. Tachiya
construction and building materials2008Vol. 2008pp. -
165
murata2008internationaltwo-dimensional
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.