Trapping and release of CO2 guest molecules by amorphous ice

Interactions of 13CO2 guest molecules with vapor-deposited porous H2O ices have been examined using temperature-programmed desorption (TPD) and Fourier transform infrared (FTIR) techniques. Specifically, the trapping and release of 13CO2 by amorphous solid water (ASW) has been studied. The use of 13CO2 eliminates problems with background CO2. Samples were prepared by (i) depositing 13CO2 on top of ASW, (ii) depositing 13CO2 underneath ASW, and (iii) codepositing 13CO2 and H2O during ASW formation. Some of the deposited 13CO2 becomes trapped when the ice film is annealed. The amount of 13CO2 trapped in the film depends on the deposition method. The release of trapped molecules occurs in two stages. The majority of the trapped 13CO2 escapes during the ASW-to-cubic ice phase transition at 165 K, and the rest desorbs together with the cubic ice film at 185 K. We speculate that the presence of 13CO2 at temperatures up to 185 K is due to 13CO2 that is trapped in cavities within the ASW film. These cavities are similar to ones that trap the 13CO2 that is released during crystallization. The difference is that 13CO2 that remains at temperatures up to 185 K does not have access to escape pathways to the surface during crystallization.