The formation of ice mantles on interstellar grains revisited – the effect of exothermicity

Abstract

Modelling of grain surface chemistry generally deals with the simulation of rare events. Usually deterministic methods or statistical approaches such as the kinetic Monte Carlo technique are applied for these simulations. All assume that the surface processes are memoryless, the Markov chain assumption, and usually also that their rates are time independent. In this paper we investigate surface reactions for which these assumptions are not valid, and discuss what the effect is on the formation of water on interstellar grains. We will particularly focus on the formation of two OH radicals by the reaction H + HO₂. Two reaction products are formed in this exothermic reaction and the resulting momentum gained causes them to move away from each other. What makes this reaction special is that the two products can undergo a follow-up reaction to form H₂O₂. Experimentally, OH has been observed, which means that the follow-up reaction does not proceed with 100% efficiency, even though the two OH radicals are formed in each other's vicinity in the same reaction. This can be explained by a combined effect of the directionality of the OH radical movement together with energy dissipation. Both effects are constrained by comparison with experiments, and the resulting parametrised mechanism is applied to simulations of the formation of water ice under interstellar conditions.