Ab Initio Model Study of the Mechanism of Hydrogen Chloride Ionization on Ice:  Reactivity of C₃O₂ with Ionized HCl

Abstract

The heterogeneous reaction of HCl on an ice surface, which is relevant in atmospheric and stratospheric chemistry, is discussed from a theoretical approach. A proton transfer mechanism is proposed for HCl ionization on amorphous ice surfaces leading to a solvent separated ion pair. The reactivity of ionized hydrochloric acid on carbon suboxide (C 3 O 2 ) is studied as an example and in connection with our earlier experimental work. The role of the ice environment on the structure and polarization of the suboxide molecule is elucidated and a theoretical model is proposed for the synthesis of chloroformylketene.