Exploiting single photon vacuum ultraviolet photoionization to unravel the synthesis of complex organic molecules in interstellar ices

Complex organic molecules (COM) such as aldehydes, ketones, carboxylic acids, esters, and amides are ubiquitous in the interstellar medium, but traditional gas phase astrochemical models cannot explain their formation routes. By systematically exploiting on line and in situ vacuum ultraviolet photoionization coupled with reflectron time of flight mass spectrometry (PI-ReTOF-MS) and combining these data with infrared spectroscopy (FTIR), we reveal that complex organic molecules can be synthesized within interstellar ices that are condensed on interstellar grains via non-equilibrium reactions involving suprathermal hydrogen atoms at temperatures as low as 5 K. By probing for the first time specific structural isomers without their degradation (fragment-free), the incorporation of tunable vacuum ultraviolet photoionization allows for a much greater understanding of reaction mechanisms that exist in interstellar ices compared to traditional methods, thus eliminating the significant gap between observational and laboratory data that existed for the last decades. With the commission of the Atacama Large Millimeter/ Submillimeter Array (ALMA), the number of detections of more complex organic molecules in space will continue to grow - including biorelevant molecules connected to the Origins of Life theme - and an understanding of these data will rely on future advances in sophisticated physical chemistry laboratory experiments. Published by Elsevier B.V.