Large Isotope Effects in Tunneling Chemical Reactions

Abstract

Our studies on the isotope effects in tunneling reactions are autoreviewed. Large isotope effects are observed in tunneling reactions, which take place by passing through the potential energy barrier for a reaction. A very large isotope effect more than 3×104 was obtained in tunneling reactions H(D)±H2(D2) in γrays-irradiated solid hydrogen at 4.2K, though there is no isotope effect in a hot atom reaction. The isotope effect on H2 or D2 detachment from a 2,3-dimethylbutane cation, produced by γ-radiolysis, amounts to a very large value of 1.7×104 at 77K that indicates a tunneling detachment of a hydrogen molecule. The tunneling reaction of tritium atoms, produced by a 3He(n, p)T reaction, with H2 or D2 in liquid helium at 1.3 K shows a large isotope effect of 150. A large isotope effect (≥20–50) was observed in the tunneling reaction of vitamin C and the long-lived protein radicals in biological systems. It is concluded that large isotope effects caused by a tunneling reaction play a role in radiation chemistry, a nuclear fusion technology and radiation biology.