Diabatic electron transfer free energy surfaces

Fig. 1. The Marcus parabolic free energy surfaces corresponding to the reactant electronic state of the system (DA) and to the product electronic state of the system (D A ) cross (become resonant) at the transition state. The curves which cross are computed with zero electronic tunneling interaction and are known as the diabatic curves, and include the Born-Oppenheimer potential energy of the molecular system plus the environmental polarization free energy as a function of the reaction coordinate. Due to the finite electronic coupling between the reactant and charge separated states, a fraction k l of the molecular systems passing through the transition state region will cross over onto the product surface this electronically controlled fraction k l thus enters directly as a factor into the electron transfer rate constant...

The two-dimensional electron transfer diabatic free energy surfaces in Figure 7 have been analyzed with the Golden Rule rate expression given in Eq. 46. This analysis suggests that FT and EPT are possible for both systems, but FT is the dominant path due to significant overlap between the proton vibrational wave... 

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