Ethane cation decomposition characterization by EBMI spectroscopy: gas‐phase dissociative recombination as a source of secondary products

The decomposition products of the d₆‐ethane cation following charge‐transfer ionization with Ar⁺, under conditions of varying ionization electron current, have been isolated in solid argon matrices at 18 K and examined using Fourier transform infrared spectroscopy. Gas samples containing 1 : 1600 d₆‐ethane : Ar were subjected to electron bombardment by using either a high (pin) or a low (plate) ionization density anode configuration with ionization currents between 20 and 150 μA. Under high ionization density conditions, the observed major products were d₄‐ethene (C₂D₄) and d₂‐acetylene (C₂D₂), with smaller yields of C₂D₅, C₂D₃, and C₂D. The yield of each dehydrogenation product was enhanced with increased current. Analogous experiments employing the low ionization density plate anode resulted in reduced C₂D₆ destruction and the formation of only C₂D₄ and C₂D₂. The results suggest the onset of dissociative recombination processes under high ion density conditions. In this context, the results can be interpreted as a dissociative recombination of primary ion products, which gives rise to further dehydrogenation, and appearance of additional neutral radical products. Copyright © 2012 John Wiley & Sons, Ltd.