Adiabatic Proton Transfer Free Energy Relationship FER

Adiabatic Proton Transfer Free Energy Relationship (FER) 

We now turn to a detailed discussion of the activation free energy AG which determines the adiabatic PT TSTrate constant Eq. (10.4). In particular, we discuss the derived activation free energy-reaction free energy relation Eq. (10.5) and its components, in a molecular description. We focus on transfer of a proton, but include some aspects for deuteron transfer in preparation for a discussion of KIEs in Section 10.2.3. 

We begin with an overview of the total free energy of the reacting system versus the solvent reaction coordinate, which can be usefully decomposed into two basic contributions [3, 7], as shown in Fig. 10.3(b), 

These are respectively, a bare free energy, corresponding to the situation 

We now turn to the individual components of the FER in Eq. (10.5). These are AGlg, the intrinsic reaction barrier AGl , = AG1(AGrxn = for the thermody- 

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