Thermal Desorption Kinetics, Binding Energies, and Entrapment of Methyl Mercaptan Ices (2504.01102v1)

Abstract: Organosulfur species are potential major carriers of sulfur in the interstellar medium, as well as interesting ingredients in prebiotic chemistry. The most fundamental question regarding these species is under which conditions they reside in the gas versus solid phase. Here, we characterize the thermal desorption kinetics, binding energies, and entrapment of the organosulfur methyl mercaptan (CH$_3$SH, or MeSH) in different ice environments, comparing them with those of methanol (CH$_3$OH, or MeOH) ices. The derived multi-layer (pure MeSH-MeSH) and sub-monolayer (layered MeSH-H$_2$O) binding energies are surprisingly similar, corresponding to snow line locations where the disk midplane temperature is ~105 K. In both H$_2$O-dominated and more realistic H$_2$O:CO$_2$-dominated ices, 100% of the MeSH is entrapped, almost exclusively desorbing at the molecular volcano desorption peak, indicating that MeSH is retained at the water snow line if initially mixed with water ice during formation. Additionally, the presence of MeSH in an ice mixture enhances the entrapment of CO$_2$ and MeOH (up to 100%) until the onset of volcano desorption; without MeSH, both desorb at their respective pure desorption temperatures and also co-desorb with water. Compared to MeOH, MeSH binds less well to water, explaining why MeSH escapes during water ice crystallization rather than co-desorbing with water. These results show the larger relative size of MeSH compared to MeOH significantly impacts its ability to bind to water and its entrapment efficiency. Therefore, molecular size plays an important role in the adsorption and retention of S-bearing organics and, in turn, other volatiles in ices.