Electron-Induced Synthesis of Dimethyl Ether in the Liquid-Vapor Interface of Methanol.

Ether synthesis from alcohol is known to be acid-catalyzed. Such a process could happen in the acidified liquid of alcohol, but hitherto lacking the experimental evidence. Here we demonstrate that dimethyl ether is spontaneously synthesized in the liquid-vapor interface of pure methanol after ionizing radiation with electrons. Using time-delayed tandem mass spectrometry measurements in combination with theoretical calculations, we further confirm that the protonated dimethyl ether is produced from the ion-molecule reactions not only in the dense vapor above the interface but also within the molecular clusters of the acidic interface. Our finding provides a convincing piece of evidence about the liquid-vapor interfacial acidification by the electron-impact ionizing radiation, exhibiting a promising way to control the chemical reactions in the liquid surface.