Abstract

Kinetic isotope effects reveal mechanistic insight into chemical reactions. Larger isotope ratios often lead to larger changes in rate, and, commonly, the largest ratio is 2—for the substitution of deuterium for hydrogen. Fleming et al. (p. [448][1]; see the Perspective by [Alexander][2] ) compared results for the simplest chemical reaction, of an H atom with H2, for two hydrogen isotopes created with positive and negative muons, which provide an unprecedentedly large mass ratio of 36. At 500 kelvin, the relative reaction rates measured agreed with those calculated using variational transition state theory. [1]: /lookup/doi/10.1126/science.1199421 [2]: /lookup/doi/10.1126/science.1201509

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