Nonadiabatic Proton Transfer Kinetic Isotope Effects

Nonadiabatic Proton Transfer Kinetic Isotope Effects 

---

Nonadiabatic Proton Transfer Kinetic Isotope Effects... 

In summary, although the BH model predicts an inverted region for the kinetics of proton in the nonadiabatic regime, the BH model is only in qualitative accord with the data derived from the proton transfer within the benzophenone-N, A -dimethylaniline contact radical ion pairs. The failure of the model lies in its ID nature as it does not take into account the degrees of freedom for the vibrations associated with the proton-transfer mode. By incorporating these vibrations into the BH model, the LH model provides an excellent account of the parameters serving to control the kinetics of nonadiabatic proton transfer. A more rigorous test for the LH model will come when the kinetic deuterium isotope effects for benzophenone-A, A -dimethylaniline contact radical ions are examined as well as the temperature dependence of these processes are measured. 

Kiefer, P. and Hynes, J. (2004). Kinetic isotope effects for nonadiabatic proton transfer reactions in a polar environment 1 Interpretation of tunneling kinetic isotopic effects. J. Phys. Chem. A. 108, 11793-11808... 

Kiefer, P. M., Hynes, J. T. (2006) Interpretation of primary kinetic isotope elfects for adiabatic and nonadiabatic proton transfer reactions in a polar environment, in Isotope Effects in Chemistry and Biology,... 

---