Trapping of hydrochloric and hydrofluoric acid at vacancies on and underneath the ice I(h) basal-plane surface

We investigate the uptake of HCl and HF at lattice vacancies in ice Ih as a function of their distance to the basal-plane surface layer using density-functional theory calculations. The results for HCl display large dispersions in the binding-energy results due to the appearance of distinct dissociation states. The layer-averaged results suggest that the uptake of HCl is most favorable in the two layers just below the surface, which is consistent with available experimental indications. The behavior of HF is found to be manifestly different due to the fact that it is a weaker acid. The dispersion in the binding-energy values is significantly less compared to the case of HCl, and the average values are essentially equal to the bulk value, regardless of layer position. This suggests that, in contrast to the case of HCl, there should not be any tendency for accumulation of HF near the surface.