A deuterium-hydrogen fractionation mechanism in magnesium oxide

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Scientific paper

Water dissolved in a nominally anhydrous oxide like MgO forms not only OH - ions, as is usually assumed, but also molecular H 2 and peroxy anions O 2 2- . The specific lattice site where this reaction occurs has been identified for the model-type MgO structure: it is the fully OH - compensated cation vacancy. In partially deuterated synthetic MgO, molecular D 2 forms preferentially to H 2 , by a factor of the order of 4. Three methods have been used to study this very large D/H fractionation experimentally: mass spectrometry, electron spin resonance and infrared spectroscopy. All give consistent results and confirm that internal D/H fractionation occurs and is a function of the temperature. Theoretically the D/H fractionation is explained by the lower zeropoint energy of D 2 with respect to H 2 , amplified by secondary processes through which the molecular hydrogen species become mobilized and eventually lost via diffusion. The possible consequences of such internal D/H fractionation processes are indicated for the interpretation of water and hydrogen release patterns, with varying D/H ratios, from terrestrial and extraterrestrial samples.

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