Direct D-atom Incorporation in Radicals: An Overlooked Pathway for Deuterium Fractionation

Direct D-H exchange in radicals is investigated in a quasi-uniform flow employing chirped-pulse millimeter-wave spectroscopy. Inspired by the H-atom catalyzed isomerization of C3H2 reported in our previous study, D-atom reactions with the propargyl (C3H3) radical and its photoproducts were investigated. We observed very efficient D-atom enrichment in the photoproducts through an analogous process of D addition/H elimination to C3H2 isomers occurring at 40 K or below. Cyclic C3HD is the only deuterated isomer observed, consistent with the expected addition/elimination yielding the lowest energy product. The other expected addition/elimination product, deuterated propargyl, is not directly detected, although its presence is inferred by the observations in the latter part of the flow. There, in the high-density region of the flow, we observed both isotopomers of singly deuterated propyne attributed to stabilization of the H+C3H2D or D+C3H3 adducts. The implications of these observations for the deuterium fractionation of hydrocarbon radicals in astrochemical environments is discussed with the support of a monodeuterated chemical kinetic model.