The release of trapped gases from amorphous solid water films. II. "Bottom-up" induced desorption pathways

In this (Paper II) and the preceding companion paper (Paper I; R. May, R. Smith, and B. Kay, J. Chem. Phys. 138, 104501 (2013)), we investigate the mechanisms for the release of trapped gases from underneath amorphous solid water (ASW) films. In Paper I, we focused on the low coverage regime where the release mechanism is controlled by crystallization-induced cracks formed in the ASW overlayer. In that regime, the results were largely independent of the particular gas underlayer. Here in Paper II, we focus on the high coverage regime where new desorption pathways become accessible prior to ASW crystallization. In contrast to the results for the low coverage regime (Paper I), the release mechanism is a function of the multilayer thickness and composition, displaying dramatically different behavior between Ar, Kr, Xe, CH4, N2, O2, and CO. Two primary desorption pathways are observed. The first occurs between 100 and 150 K and manifests itself as sharp, extremely narrow desorption peaks. Temperature programmed desorption is utilized to show that these abrupt desorption bursts are due to pressure induced structural failure of the ASW overlayer. The second pathway occurs at low temperature (typically <100 K) where broad desorption peaks are observed. Desorption through this pathway is attributed to diffusion through pores formed during ASW deposition. The extent of desorption and the line shape of the low temperature desorption peak are dependent on the substrate on which the gas underlayer is deposited. Angle dependent ballistic deposition of ASW is used to vary the porosity of the overlayer and strongly supports the hypothesis that the low temperature desorption pathway is due to porosity that is templated into the ASW overlayer by the underlayer during deposition.