Unified Interpretation of Exciplex Formation and Marcus Electron Transfer on the Basis of Two-Dimensional Free Energy Surfaces†

2007 ◽  
Vol 111 (38) ◽  
pp. 9240-9248 ◽  
Author(s):  
Shigeo Murata ◽  
M. Tachiya
Keyword(s):  
Electron Transfer ◽  
Free Energy ◽  
Two Dimensional ◽  
Exciplex Formation ◽  
Energy Surfaces

scholarly journals Two-Dimensional Free Energy Surfaces for Electron Transfer Reactions in Solution

2008 ◽  
Vol 2008 ◽  
pp. 1-8 ◽  
Author(s):  
Shigeo Murata ◽  
Maged El-Kemary ◽  
M. Tachiya
Keyword(s):  
Electron Transfer ◽  
Free Energy ◽  
Nonpolar Solvent ◽  
Final States ◽  
Free Energies ◽  
Intermolecular Electron Transfer ◽  
Exciplex Formation ◽  
Orientational Polarization ◽  
Distance Dependence ◽  
Energy Surfaces

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.

Modeling the free energy surfaces of electron transfer in condensed phases

2000 ◽  
Vol 113 (13) ◽  
pp. 5413 ◽  
Author(s):  
Dmitry V. Matyushov ◽  
Gregory A. Voth
Keyword(s):  
Electron Transfer ◽  
Free Energy ◽  
Condensed Phases ◽  
Energy Surfaces
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