Kinetic Isotope Effect Magnitude and Variation with Reaction Asymmetry

1 Kinetic Isotope Effect Magnitude and Variation with Reaction Asymmetry 

Before presenting the KIE variation with reaction asymmetry for nonadiabatic PT, it will prove useful to first discuss the individual isotope PT rate constant Eq. (10.36) s variation with reaction asymmetry, which must include tunneling prefactor terms as well as the activation free energy. This behavior was analyzed up through quadratic terms in [5] to find 

This analysis anticipates that the 0-0 rate kiQQ will have a significant contribution near AGj xn titl thus the rate expression in Eq. (10.36) can be written 

is the difference between the general reaction barrier AgI Eq. (10.38) 

The Br0nsted coefficient dial its derivative d i in Eq. (10.41) can thus be ivritten as a sum of the 0-0 case plus a correction due to the contribution of excited proton vibrational transitions  

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