Using Laboratory Investigations to Aid the Identification of Small Aromatic Molecules in Water-Containing Astrophysical Ices

Monocyclic aromatic hydrocarbons such as benzene, toluene and xylene are thought to play an important role as precursors to the formation of polycyclic aromatic hydrocarbons (PAHs) and their methylated counterparts in a range of astrophysical environments. Benzene has been detected in two carbon rich objects and models have predicted that it could also be present in the interstellar medium (ISM). It has hence been speculated that small aromatic molecules are present in molecular clouds in the ISM, although they have not been detected to date. If they are present in the ISM, they are likely to exist in water-ice dominated icy mantles on the surface of dust grains.We present a laboratory study of benzene, toluene and two xylene isomers (ortho- and para-xylene) in the presence of water ice on a carbonaceous model dust grain surface (highly oriented pyrolytic graphite, HOPG). Temperature programmed desorption (TPD) shows how the desorption of the molecules is affected by the presence of water ice. The importance of these data for astrophysical situations is demonstrated by the use of TPD-derived kinetic parameters to generate a simple model of desorption in dense molecular clouds on an astrophysical timescale. Since benzene, toluene and xylene have not been detected in water-dominated icy mantles to date, desorption has been simulated in a range of different water-containing environments to show the different behaviour expected depending on ice composition. The simulations demonstrate how future observations of aromatic molecules in dense molecular clouds at known temperatures could reveal which environments the molecules are in. Data from these experiments are also used to predict the behaviour of other, larger, aromatic molecules such as PAHs. Reflection absorption infrared spectroscopy (RAIRS) is also used to record the infrared spectra of the small molecules in different water ice configurations. These spectra can be used to aid identification of these icy aromatics in future observations, such as those that will be possible with the James Webb Space Telescope (JWST). In all cases, spectra of mixed ices consisting of the aromatic molecule and amorphous water ice show evidence of interactions between the water ice and the aromatic species.

Time-scales to reach chemical equilibrium in ices at snowline distance around compact objects: the influence of accretion mass in the central object

ABSTRACT In this work, we analyse soft X-ray emission due to mass accretion on to compact stars and its effects on the time-scale to reach chemical equilibrium of eventual surrounding astrophysical ices exposed to that radiation. Reaction time-scales due to soft X-ray in water-rich and pure ices of methanol, acetone, acetonitrile, formic acid, and acetic acid were determined. For accretion rates in the range $\dot{m}=10^{-12}\!-\!10^{-8}\,{\rm M}_\odot$ yr−1 and distances in the range 1–3 LY from the central compact objects, the time-scales lie in the range 10–108 yr, with shorter time-scales corresponding to higher accretion rates. Obtained time-scales for ices at snow-line distances can be small when compared to the lifetime (or age) of the compact stars, showing that chemical equilibrium could have been achieved. Time-scales for ices to reach chemical equilibrium depend on X-ray flux and, hence, on accretion rate, which indicates that systems with low accretion rates may not have reached chemical equilibrium.

Thermal and photochemical study of CH3OH and CH3OH–O2 astrophysical ices

ABSTRACT Methanol, which is one of the most abundant organic molecules in the interstellar medium, plays an important role in the complex grain surface chemistry that is believed to be a source of many organic compounds. Under energetic processing such as ultraviolet (UV) photons or cosmic rays, methanol may decompose into CH4, CO2, CO, HCO, H2CO, CH3O and CH2OH, which in turn lead to complex organic molecules such as CH3OCHO, CHOCH2OH and HOCH2CH2OH through radical recombination reactions. However, although molecular oxygen and its detection, abundance and role in the interstellar medium have been the subject of many debates, few experiments on the oxidation of organic compounds have been carried out under interstellar conditions. The present study shows the behaviour of solid methanol when treated by UV light and thermal processing in oxygen-rich environments. Methanol has been irradiated in the absence and presence of O2 at different concentrations in order to study how oxidized complex organic molecules may form and also to investigate the O-insertion reaction in the C–H bound to form methanediol HOCH2OH through a CH3OH + O(1D) solid-state reaction. The adding of O2 in the thermal and photochemical reaction of solid methanol leads to the formation of O3, H2O and HO2, in addition to three main organics, HCOOH, CHOCHO and HOCH2OH. We show that in an O2-rich environment, species such as CO, CH4, HCO, CH3OH and CHOCH2OH are oxidized into CO2, CH3OH, HC(O)OO, HOCH2OH and CHOCHO, respectively, while HCOOH might be formed through the H2CO + O(3P) → (OH + HCO)cage → HCOOH hydrogen-abstraction reaction.