Phenomenological manifestations of quantum-mechanical tunneling. III. Effect on relative tritium-deuterium kinetic isotope effects

The effect of quantum-mechanical tunneling on relative tritium-deuterium kinetic isotope effects is investigated with the aid of model calculations. It is shown that even when tunneling is important, such relative effects, defined as r=ln(kH/kT) [ln(kH/kD)]−1, have values not very different from the...

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Published in:The Journal of chemical physics 1974-04, Vol.60 (7), p.2815-2821
Main Authors: Stern, Marvin J., Weston, Ralph E.
Format: Article
Language:English
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Summary:The effect of quantum-mechanical tunneling on relative tritium-deuterium kinetic isotope effects is investigated with the aid of model calculations. It is shown that even when tunneling is important, such relative effects, defined as r=ln(kH/kT) [ln(kH/kD)]−1, have values not very different from their values in the absence of tunneling. Thus, for the types of reactions commonly used to investigate tunneling, the limits 1.33 ≤ r ≤ 1.58 are not likely to be exceeded. There is no direct general correlation between the magnitude of r and the extent of tunneling; the temperature dependence of r is qualitatively the same for a wide range of reaction models and barrier heights.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1681449