Chemical Reactivity of Strongly Interacting, Hydrogen-Bond-Forming Molecules Following 193 nm Photon Irradiation: Methanol in Amorphous Solid Water at Low Temperatures.

Mixtures of methanol and amorphous solid water (ASW) ices are observed in the interstellar medium (ISM), where they are subject to irradiation by UV photons and bombardment by charged particles. The charged particles, if at high enough density, induce a local electric field in the ice film that potentially affects the photochemistry of these ices. When CD 3 OD@ASW ices grown at 38 K on a Ru(0001) substrate are irradiated by 193 nm (6.4 eV) photons, products such as HD, D 2 , CO, and CO 2 are formed in large abundances relative to the initial amount of CD 3 OD. Other molecules such as D 2 O, CD 4 , acetaldehyde, and ethanol and/or dimethyl ether are also observed, but in smaller relative abundances. The reactivity cross sections range from (2.6 ± 0.3) × 10 -21 to (3.8 ± 0.3) × 10 -25 cm 2 /photon. The main products are formed through two competing mechanisms: direct photodissociation of methanol and water and dissociative electron attachment (DEA) by photoelectrons ejected from the Ru(0001) substrate. An electric field of 2 × 10 8 V/m generated within the ASW film during Ne + ions bombardment is apparently not strong enough to affect the relative abundances (selectivity) of the photochemical products observed in this study.