Electron-induced chemistry of methyl chloride caged within amorphous solid water

Abstract

The interaction of low energy electrons (1.0-25 eV) with methyl-chloride (CD3Cl) molecules, caged within Amorphous Solid Water (ASW) films, 10-120 monolayer (ML) thick, has been studied on top of a Ru(0001) substrate under Ultra High Vacuum (UHV) conditions. While exposing the ASW film to 3 eV electrons a static electric field up to 8 × 10(8) V∕m is developed inside the ASW film due to the accumulation of trapped electrons that produce a plate capacitor voltage of exactly 3 V. At the same time while the electrons continuously strike the ASW surface, they are transmitted through the ASW film at currents of ca. 3 × 10(-7) A. These electrons transiently attach to the caged CD3Cl molecules leading to C-Cl bond scission via Dissociative Electron Attachment (DEA) process. The electron induced dissociation cross sections and product formation rate constants at 3.0 eV incident electrons at ASW film thicknesses of 10 ML and 40 ML were derived from model simulations supported by Thermal Programmed Desorption (TPD) experimental data. For 3.0 eV electrons the CD3Cl dissociation cross section is 3.5 × 10(-16) cm(2), regardless of ASW film thickness. TPD measurements reveal that the primary product is deuterated methane (D3CH) and the minor one is deuterated ethane (C2D6).