Abstract
The reaction between methanol radical cations and methane, producing methyl radicals and protonated methanol, is pivotal to both astrochemical and atmospheric processes. Methanol and methane are the most abundant organic molecules in space and Earth's atmosphere and central to molecular synthesis under different environmental conditions. Here, we present a combined experimental and theoretical investigation of the ion-molecule reaction between CH(3)OH(•+) and CH(4). The study explores the reaction mechanism and energetics under ionized conditions utilizing quantum chemical methods and experimental data. The findings reveal that the reaction's non-thermal behavior becomes pronounced when CH(3)OH(•+) is vibrationally excited by photon absorption above the ionization threshold, as can happen in the presence of ionizing agents like cosmic rays. Conversely, in thermal equilibrium conditions, the reaction accelerates as temperatures decrease, as suggested by canonical rate coefficient calculations. The products can initiate further chemical reactions, shaping molecular networks in the interstellar medium and affecting atmospheric trace gas balances.