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Three structural isomers of the C2H4O2 molecule, namely, methyl formate (MF;HCOOCH3), acetic acid (AA; CH3COOH), and glycol aldehyde (GA; HOCH2CHO), haveattracted considerable attention as targets for understanding pathways towardsmolecular complexity in the interstellar medium (ISM). Among these isomers, MFis decisively abundant in various astronomical objects. For various formationpathways of MF, surface reactions on cosmic dust would play an important role.However, when compared to observations, the formation of MF has been found tobe relatively inefficient in laboratory experiments in which methanol(CH3OH)-dominant ices were processed by ultraviolet (UV) photons and cosmic-rayanalogues. Here, we show experimental results on the effective formation of MFby the photolysis of CH3OH on water ice at 10 K. We found that the keyparameter leading to the efficient formation of MF is the supply of OH radicalsby the photolysis of H2O, which significantly differs from CH3OH-richexperimental conditions. Moreover, using an ultra-high-sensitivity surfaceanalysis method, we succeeded in constraining the decisive formation pathway ofMF via the photolysis of methoxymethanol (MM; CH3OCH2OH), which would improveour current understanding of chemical evolution in the ISM.

Efficient formation pathway of methyl formate: the role of OH radicals on ice dust