Trapping and desorption of complex organic molecules in water at 20 K.

The formation, chemical, and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate, and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence, the interaction of these species with water ice is crucially important in dictating their behaviour. Here, we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H, and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices.

Adsorption and Thermal Processing of Glycolaldehyde, Methyl Formate, and Acetic Acid on Graphite at 20 K.

We present the first detailed comparative study of the adsorption and thermal processing of the three astrophysically important C2O2H4 isomers glycolaldehyde, methyl formate, and acetic acid adsorbed on a graphitic grain analogue at 20 K. The ability of the individual molecule to form intermolecular hydrogen bonds is extremely important, dictating the growth modes of the ice on the surface and the measured desorption energies. Methyl formate forms only weak intermolecular bonds and hence wets the graphite surface, forming monolayer, bilayer, and multilayer ices, with the multilayer having a desorption energy of 35 kJ mol(-1). In contrast, glycolaldehyde and acetic acid dewet the surface, forming clusters even at the very lowest coverages. The strength of the intermolecular hydrogen bonding for glycolaldehyde and acetic acid is reflected in their desorption energies (46.8 and 55 kJ mol(-1), respectively), which are comparable to those measured for other hydrogen-bonded species such as water. Infrared spectra show that all three isomers undergo structural changes as a result of thermal processing. In the case of acetic acid and glycolaldehyde, this can be assigned to the formation of well-ordered, crystalline, structures where the molecules form chains of hydrogen-bonded moieties. The data reported here are of relevance to astrochemical studies of hot cores and star-forming regions and can be used to model desorption from interstellar ices during the warm up phase with particular importance for complex organic molecules.

Surface science investigations of the role of CO2 in astrophysical ices.

We have recorded reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) data for a range of CO2-bearing model astrophysical ices adsorbed on a graphitic dust grain analogue surface. Data have been recorded for pure CO2, for CO2 adsorbed on top of amorphous solid water, for mixed CO2:H2O ices and for CO2 adsorbed on top of a mixed CH3OH:H2O ice. For the TPD data, kinetic parameters for desorption have been determined, and the trapping behaviour of the CO2 in the H2O (CH3OH) ice has been determined. Data of these types are important as they can be used to model desorption in a range of astrophysical environments. RAIR spectra have also shown the interaction of the CO2 with H2O and CH3OH and can be used to compare with astronomical observations, allowing the accurate assignment of spectra.

Ice in space: surface science investigations of the thermal desorption of model interstellar ices on dust grain analogue surfaces.

More than 140 different molecules have been identified in the interstellar medium (ISM) to date. Dust grain particles are also found in the ISM, and some of these molecules freeze out at the cold temperatures (10-20 K) to form molecular ices. Understanding the adsorption and desorption of these ices is crucially important in understanding the processes that lead to star and planet formation, and may even help to lead to an understanding of the origin of life itself. High sensitivity surface science techniques, including temperature programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS), are being increasingly used to investigate the interactions between dust grains and interstellar ices. This perspective provides an overview of the current level of understanding of the adsorption and desorption of astrophysically relevant molecules from a range of dust grain analogue surfaces. Whilst the focus of this review is on interstellar ices, the results discussed are equally valid to discussions of cometary and planetary ices.

Thermally induced mixing of water dominated interstellar ices.

Despite considerable attention in the literature being given to the desorption behaviour of smaller volatiles, the thermal properties of complex organics, such as ethanol (C(2)H(5)OH), which are predicted to be formed within interstellar ices, have yet to be characterized. With this in mind, reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD) have been used to probe the adsorption and desorption of C(2)H(5)OH deposited on top of water (H(2)O) films of various thicknesses grown on highly oriented pyrolytic graphite (HOPG) at 98 K. Unlike many other molecules detected within interstellar ices, C(2)H(5)OH has a comparable sublimation temperature to H(2)O and therefore gives rise to a complicated desorption profile. RAIRS and TPD show that C(2)H(5)OH is incorporated into the underlying ASW film during heating, due to a morphology change in both the C(2)H(5)OH and H(2)O ices. Desorption peaks assigned to C(2)H(5)OH co-desorption with amorphous, crystalline (CI) and hexagonal H(2)O-ice phases, in addition to C(2)H(5)OH multilayer desorption are observed in the TPD. When C(2)H(5)OH is deposited beneath ASW films, or is co-deposited as a mixture with H(2)O, complete co-desorption is observed, providing further evidence of thermally induced mixing between the ices. C(2)H(5)OH is also shown to modify the desorption of H(2)O at the ASW-CI phase transition. This behaviour has not been previously reported for more commonly studied volatiles found within astrophysical ices. These results are consistent with astronomical observations, which suggest that gas-phase C(2)H(5)OH is localized in hotter regions of the ISM, such as hot cores.