Deuterium Fractionation and Ion-Molecule Reactions at Low Temperatures

Understanding deuterium fractionation is currently one of the greatest challenges in astrochemistry. In this contribution deuteration experiments of the series CH_n^+, n=2-5, in a low temperature 22-pole ion trap are used to systematically test a simple chemical rule predicting which molecular ion undergoes deuterium exchange in collisions with HD. CH_4^+ turns out to be a problem case, where prediction fails. The method of laser induced reaction (LIR) is used to determine the population ratio of the lowest ortho-to-para states of H_2D^+ relaxed in collisions with H_2. Preliminary results indicate that the ortho-to-para ratio of H_2D^+ is substantially reduced in para-H_2. This points at the important role of nuclear spin in deuterium fractionation, in particular at the destruction of ortho-H_2D^+ in collisions with ortho-H_2. More systematic LIR experiments are needed for a chemical model of deuterium fractionation including state-to-state modifications of the species involved.