The chemical processing of ethylene ices (C 2 H 4 ) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH 4 ), the C2 species acetylene (C 2 H 2 ), ethane (C 2 H 6 ), the ethyl radical (C 2 H 5 ), and-for the very first time in ethylene irradiation experiments-the C4 hydrocarbons 1-butene (C 4 H 8 ) and n-butane (C 4 H 10 ). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.
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