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Reaction kinetics

Isotope effects feel the cold

Nature Chemistry volume 6, pages 274–275 (2014)Cite this article

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Kinetic isotope effects are widely used to elucidate reaction mechanisms and are generally interpreted in terms of simple kinetic models. Measurements of this effect for the Penning ionization reaction between helium and dihydrogen highlight the need for a quantum description of chemical reaction rates when sub-kelvin temperatures are approached.

When interpreting kinetic isotope effects for gas-phase chemical reactions one often resorts to simple models of reaction rates, such as transition state theory1. These approximate theories are really only appropriate for reactions studied under relatively high-temperature conditions, at which quantum effects such as tunnelling or resonances are less important.

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Figure 1: Kinetic isotope effects at low temperature.

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Authors and Affiliations

  1. Mark Brouard is in the Department of Chemistry, University of Oxford, The Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford OX1 3QZ, UK,

    Mark Brouard

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  1. Mark Brouard
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Correspondence to Mark Brouard.

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Brouard, M. Isotope effects feel the cold. Nature Chem 6, 274–275 (2014). https://doi.org/10.1038/nchem.1903

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