Kinetic isotope effect

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In physical organic chemistry, a kinetic isotope effect (KIE) is the change in the reaction rate of a chemical reaction when one of the atoms in the reactants is replaced by one of its isotopes. Formally, it is the ratio of rate constants for the reactions involving the light (kL) and the heavy (kH) isotopically substituted reactants (isotopologues): KIE = kL/kH. This change in reaction rate is a quantum effect that occurs mainly because heavier isotopologues have lower vibrational frequencies and, therefore, lower ground-state vibrational energies, than their lighter counterparts. In most cases, this implies a greater energy input needed for heavier isotopologues to reach the transition state (or, in rare cases, dissociation limit), and therefore, a slower reaction rate. The study of KIEs can help elucidate reaction mechanisms, and is occasionally exploited in drug development to improve unfavorable pharmacokinetics by targeted replacement of metabolically vulnerable C–H bonds with "stronger...

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