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Experimental and theoretical studies are presented on the reactivity of theradical cation isomers methanimine and aminomethylene with ethyne. Selectiveisomer generation is performed via dissociative photoionization of suitableneutral precursors and via direct photoionization of methanimine. Reactivecross sections and product branching ratios are measured as a function ofphoton and collision energies. Results are discussed in light of ab initiocalculations of reaction mechanisms. The major channels, for both isomers, aredue to H atom elimination from covalently bound adducts to give [C3NH4]+.Theoretical calculations show that while for the reaction of aminomethylenewith acetylene any of the three lowest energy [C3NH4]+ isomers can form viabarrierless and exothermic pathways, for the methanimine reagent the onlybarrierless pathway is the one leading to the production of protonated vinylcyanide (CH2CHCNH+), a prototypical branched nitrile species that has beenproposed as a likely intermediate in star forming regions and in the atmosphereof Titan. The astrochemical implications of the results are briefly addressed.

frontiers in astronomy and space sciences

Experimental and computational studies on the reactivity of methanimine  radical cation (H$_2$CNH$^{+\cdot}$) and its isomer aminomethylene  (HCNH$_2^{+\cdot}$) with C$_2$H$_2$