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© 2019. The American Astronomical Society. All rights reserved.. Methoxymethanol (CH3OCH2OH) was recently detected toward the MM1 core in the high-mass star-forming region NGC 6334I. However, the underlying formation mechanisms of this complex organic molecule (COM) as well as its structural isomers ethylene glycol (HOCH2CH2OH) and the hitherto unobserved dimethyl peroxide (CH3OOCH3) are still elusive. Here, we report the very first confirmed synthesis of dimethyl peroxide - at various deuteration levels within interstellar analogous ices of D3-methanol (CD3OH) exposed to ionizing radiation at ultralow temperatures of 5 K. The discrimination of specific isomers is achieved by exploiting reflectron time-of-flight mass spectrometry coupled with isomer-selective photoionization of the subliming molecules in the temperature programmed desorption phase of the experiment. Based on the distribution of the identified species at distinct mass-to-charge ratios, we reveal primary and secondary reaction pathways to methoxymethanol, ethylene glycol, and dimethyl peroxide involving radical-radical recombination of methoxy (CH3O) and hydroxymethyl (CH2OH). Our findings help to constrain the formation mechanism of COMs detected within star-forming regions (methoxymethanol, ethylene glycol) and propose that the hitherto elusive dimethyl peroxide isomer represents an excellent candidate for future astronomical searches.

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