Figure 5.
Driving force dependence of the rate constant kPCET and the KIE for Morse (A, B) and asymmetric double well (C, D) proton potentials. In A and C, the dashed gray curves depict the rate constant calculated with only the transition from the ground reactant to the ground product vibronic state (i.e., the (0,0) vibronic state pair), whereas the solid black curves depict the rate constant including contributions from the excited proton vibrational states.. The solid gray vertical line in A and C corresponds to λ = 25 kcal/mol. In B and D, the horizontal gray lines at KIE = 1 represent the situation in which the rate constants of PCET with hydrogen and deuterium are equal.