Isotopic Hydrogen-Ion—Molecule Reactions

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Abstract
The reactions of isotopic hydrogen‐molecule ions with isotopic hydrogen molecules have been investigated using a mass spectrometer ion source as the reaction chamber. No significant differences were detected in a study of the velocity distributions of the product and reactant ions. Rate constants for the formation of H3+, D3+, and H2D++D2H+ were obtained from the reactions of H2+–H2, D2+—D2, and HD+—HD, respectively, which were in excellent agreement with theory. Isotopic fractionation was observed in the production of H2D+ and D2H+ from mixtures of H2 and D2, HD and H2, HD and D2. The isotope effects are qualitatively consistent with a more rapid formation of lower zero‐point energy intermediates.